JP2008233112A - Production method of color filter, and color filter and display unit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method of a color filter capable of forming, especially, a black image with very little variations in line widths and very finely without using a photomask, and being low in costs and excellent in display characteristics, and to provide the color filter, and a display unit. <P>SOLUTION: The production method of the color filter includes the photosensitive layer forming step of forming at least a photosensitive layer on the surface of a substrate, the exposure step of specifying a drawing element used for N-fold exposure out of usable drawing elements by using an exposure head disposed so as to form a specified set inclined angle θ with respect to the photosensitive layer, controlling the drawing elements so that the specified drawing element only is involved in exposure, and moving the exposure head in the scanning direction relatively with the photosensitive layer to carry out exposure, and the developing step of developing the exposed photosensitive layer. The color filter is produced by the production method, and the display unit uses the color filter. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a manufacturing method of a color filter suitable for a liquid crystal display device (LCD) such as a portable terminal, a portable game machine, a notebook computer, a television monitor, a PALC (plasma address liquid crystal), a plasma display, and the like, and the manufacturing method. The present invention relates to a manufactured color filter and a display device using the color filter.

The color filter is an indispensable component for a liquid crystal display (hereinafter also referred to as “LCD” or “liquid crystal display device”). This liquid crystal display is very compact, is equivalent to or better than conventional CRT displays in terms of performance, and is replacing the CRT displays.
In the formation of the color pixels of the liquid crystal display, the light passing through the color filter is colored as it is into the colors of the pixels constituting the color filter, and the light of those colors is synthesized to form a color pixel. At present, a color pixel is formed by pixels of three colors of RGB.

In recent years, the development of technology for increasing the screen size and resolution of liquid crystal displays (LCDs) has progressed, and the applications are from laptop computer displays to desktop personal computer monitors, and even television monitors (hereinafter sometimes referred to as “TV”). ). Against this background, LCDs are strongly required to reduce costs and improve display characteristics.
The direction of cost reduction is not limited to the cost reduction of materials, but the simplification of the process is in progress. In particular, the elimination of a photomask for exposure is being studied.
On the other hand, as a direction of improving display characteristics, high definition and the like in which the number of pixels per inch is increased are being studied.
In particular, since the black matrix formed so as to define the pixels of the three colors of RGB defines the apparent pixel width, the variation in the line width of the black matrix depends on the periodicity, such as moire and It tends to cause display unevenness such as periodic unevenness. Therefore, there is a demand for a method capable of forming a fine pattern of a black image forming a black matrix with high definition.

As a method for forming such a color filter, a photolithography method is generally known in which a fine pattern is formed by exposing and developing a photosensitive composition.
As an exposure apparatus for performing the photolithography method, patterning is performed by directly scanning laser light such as a semiconductor laser or a gas laser on the photosensitive composition based on digital data such as a pattern without using a photomask. An exposure apparatus using a laser direct imaging system (hereinafter sometimes referred to as “LDI”) has been studied (for example, see Non-Patent Document 1 and Patent Document 1).

  In the exposure head of the exposure apparatus, a single exposure may be performed depending on the configuration of the light source array, such as when a digital micromirror device (DMD) having a generally available size is used as the spatial light modulation element. It is difficult to cover a sufficiently large exposure area with the head. Therefore, there has been proposed an exposure apparatus in which a plurality of the exposure heads are used in parallel and the exposure heads are inclined with respect to the scanning direction.

For example, in Patent Document 2, a plurality of exposure heads each having a DMD in which micromirrors are arranged in a rectangular lattice shape are inclined with respect to the scanning direction, and triangular portions on both sides of the inclined DMD are provided as follows: An exposure apparatus is described in which each exposure head is mounted in such a manner that the DMDs adjacent to each other in the direction orthogonal to the scanning direction complement each other.
In Patent Document 3, a plurality of exposure heads having a rectangular grid DMD are not tilted with respect to the scanning direction or tilted by a small angle, and exposure is performed by a DMD adjacent in a direction perpendicular to the scanning direction. Each exposure head is mounted with a setting such that the regions overlap each other by a predetermined width, and the number of micromirrors to be driven is gradually decreased or increased at a certain rate at a portion corresponding to the overlapping portion between the exposure regions of each DMD. An exposure apparatus is described in which the exposure area of each DMD has a parallelogram shape.

  However, when exposure is performed with a plurality of exposure heads inclined with respect to the scanning direction, it is generally difficult to finely adjust the relative position and relative mounting angle between the exposure heads. There is a problem that it shifts slightly.

On the other hand, in order to improve the resolution, the exposure head is used so that the scanning line of the light beam from one picture element unit coincides with the scanning line of the light beam from another picture element unit. There has been proposed an exposure apparatus of a multiple exposure type in which each point on the surface to be exposed is exposed by overlapping substantially a plurality of times.
For example, Patent Document 4 discloses that a plurality of micromirrors (picture element units) are provided in order to improve the resolution of a two-dimensional pattern formed on an exposure surface and to express a pattern including a smooth diagonal line. An exposure apparatus is described in which rectangular DMDs arranged in a dimension are inclined with respect to the scanning direction so that exposure spots from adjacent micromirrors partially overlap on the exposure surface.
Further, Patent Document 5 uses a rectangular DMD that is inclined with respect to the scanning direction to superimpose exposure spots on the exposure surface to change the total illumination chromaticity, An exposure apparatus capable of suppressing an imaging error due to a factor such as a partial defect of a microlens is described.

However, even in the case of performing the multiple exposure, the exposure head density and arrangement at the location on the exposed surface of the photosensitive layer to be exposed, due to the mounting angle of the exposure head deviating from an ideal setting inclination angle. However, it is different from other portions, and there is a problem that the resolution and density of the image formed on the pattern forming material are uneven, and the edge roughness is increased in the formed pattern.
Furthermore, it is caused not only by a shift in the mounting position and mounting angle of the exposure head, but also by various aberrations of the optical system between the image element and the exposed surface of the photosensitive layer, distortion of the image element itself, and the like. Pattern distortion also causes unevenness in the resolution and density of the pattern formed on the exposed surface of the photosensitive layer.

  In order to solve these problems, a method for improving the adjustment accuracy of the mounting position and angle of the exposure head, the adjustment accuracy of the optical system, and the like can be considered. However, if improvement in accuracy is pursued, the manufacturing cost becomes very high. There is a problem of end. Similar problems can occur not only in the exposure apparatus but also in various drawing apparatuses such as an ink jet printer.

  Therefore, the displacement of the mounting position and mounting angle of the exposure head, the various aberrations of the optical system between the image element portion and the exposure surface of the photosensitive layer, the pattern distortion caused by the distortion of the image element portion itself, etc. By leveling the influence of the variation in exposure amount due to the above, and reducing the variation in the resolution and density of the pattern formed on the exposed surface of the photosensitive layer, in particular, the line width variation of the black image is extremely small, A method of manufacturing a color filter capable of forming with high definition, a color filter having excellent display characteristics manufactured by the method of manufacturing the color filter, and a method of forming a display device color filter using the color filter are still provided. However, the present situation is that further improved development is desired.

JP 2004-1244 A Japanese Patent Laid-Open No. 2004-9595 JP 2003-195512 A US Pat. No. 6,493,867 Special table 2001-500628 gazette Akihito Ishikawa "Development shortening and mass production application by maskless exposure", "Electrotronics packaging technology", Technical Research Committee, Vol.18, No.6, 2002, p.74-79

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention does not use a photomask, the displacement of the mounting position and mounting angle of the exposure head, various aberrations of the optical system between the image element and the exposed surface of the photosensitive layer, and the By leveling the influence of variation in exposure amount due to pattern distortion caused by distortion etc. of the picture element itself, and reducing variation in resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer, Especially, the line width variation of the black image is extremely small, can be formed with high definition, low cost, and excellent display characteristics. For liquid crystal display devices (LCD) such as portable terminals, portable game machines, notebook computers, TV monitors, Manufacturing method of color filter suitably used for PALC (plasma address liquid crystal), plasma display, etc., and manufacturing method of the color filter示特 excellent in color filters, as well as an object to provide a display device using the color filter.

Means for solving the problems are as follows. That is,
<1> A photosensitive layer forming step of forming at least a photosensitive layer on the surface of a substrate using a photosensitive composition containing a binder, a polymerizable compound, a colorant, and a photopolymerization initiator,
For the photosensitive layer,
A light irradiating means, and n (where n is a natural number of 2 or more) two-dimensionally arranged picture elements that receive and emit light from the light irradiating means, and according to the pattern information, An exposure head provided with a light modulation means capable of controlling a picture element portion, the exposure head being arranged so that a column direction of the picture element portion forms a predetermined set inclination angle θ with respect to a scanning direction of the exposure head Using the head
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
An exposure step of performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction; and
And a developing step of developing the photosensitive layer exposed in the exposing step. In the method for producing a color filter according to <1>, N exposure (N is a natural number of 2 or more) among the usable pixel parts by the used pixel part designating unit for the exposure head. ) Is specified, and the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in the exposure. The By performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction, the exposure head is formed on the exposed surface of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head. Variations in the resolution of the pattern and unevenness in density are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<2> The exposure is performed by a plurality of exposure heads, and the drawing element specifying means is related to the exposure of the head-to-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The method for manufacturing a color filter according to <1>, wherein, among the element parts, the image element part used for realizing N double exposure in the inter-head connection region is designated. In the method for producing a color filter according to <2>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads. The position of the exposure head is determined by designating the pixel part to be used for realizing N double exposure in the head-to-head connection area among the picture-element parts involved in the exposure of the head-to-head connection area. Variations in the resolution and density unevenness of the pattern formed in the connection area between the heads on the exposed surface of the photosensitive layer due to the mounting angle deviation are averaged. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<3> The exposure is performed by a plurality of exposure heads, and the used picture element specifying means is involved in exposure other than the inter-head connection region that is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The method for producing a color filter according to <2>, wherein the image element part used for realizing N double exposure in an area other than the inter-head connection area among the image element parts is designated. In the method for producing a color filter according to <3>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads. Among the picture element parts involved in exposure other than the inter-head connecting area, the picture element part used for realizing the N-fold exposure outside the inter-head connecting area is designated, whereby the exposure head Variations in the resolution and density unevenness of the pattern formed in areas other than the joint area between the heads on the exposed surface of the photosensitive layer due to deviations in the mounting position and mounting angle are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<4> When the set inclination angle θ is N, the number of N exposures, the number s of pixel parts in the column direction, the interval p of the pixel parts in the column direction, and the exposure head tilted. the relative row direction pitch δ of pixel parts in the direction perpendicular to the scanning direction, the following equation with respect to theta _ideal satisfying spsinθ _ideal ≧ Nδ, which is set so as to satisfy the relation of θ ≧ θ _ideal < The color filter manufacturing method according to any one of <1> to <3>.
<5> The method for producing a color filter according to any one of <1> to <4>, wherein N in N-fold exposure is a natural number of 3 or more. In the method for producing a color filter according to <5>, multiple drawing is performed when N in N double exposure is a natural number of 3 or more. As a result, due to the effect of filling, variations in the resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to a shift in the mounting position and mounting angle of the exposure head are more precisely leveled.

<6> Use pixel part designation means
A light spot position detecting means for detecting a light spot position as a pixel unit that is generated by the picture element unit and constitutes an exposure area on the exposed surface;
<1> to <5>, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing N double exposure based on a detection result by the light spot position detection unit. It is a manufacturing method of a color filter.
<7> The color filter production according to any one of <1> to <6>, wherein the used pixel part specifying unit specifies, in line units, the used pixel part used for realizing the N double exposure. Is the method.

<8> Based on at least two light spot positions detected by the light spot position detection means, the column direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted <6> to <7>, wherein the inclination angle θ ′ is specified, and the drawing element selection means selects the drawing element part so as to absorb the error between the actual inclination angle θ ′ and the set inclination angle θ. It is a manufacturing method of the color filter in any one.
<9> The average inclination angle θ ′ is an average value, a median value, and a plurality of actual inclination angles formed by the row direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined. It is a manufacturing method of the color filter as described in said <8> which is either the maximum value and the minimum value.
<10> The pixel part selection means derives a natural number T close to t that satisfies the relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <8> to <9> for selecting the pixel part from the first line to the T-th line in a line element (where m represents a natural number of 2 or more) arranged as a used pixel part The method for producing a color filter according to any one of the above.
<11> The pixel part selection means derives a natural number T close to t that satisfies the relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m In the picture element part arranged in a row (where m represents a natural number of 2 or more), the picture element part from line (T + 1) to m-th line is specified as an unused picture element part, and the unused picture element part is specified. The method for producing a color filter according to any one of <8> to <9>, wherein the picture element part excluding the element part is selected as a use picture element part.

<12> In a region including at least an overlapped exposure region on an exposed surface formed by a plurality of pixel part columns,
(1) Means for selecting a used pixel portion so that a total area of an overexposed region and an underexposed region is minimized with respect to an ideal N-fold exposure;
(2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area and the number of pixel units in an underexposed area are equal to each other with respect to an ideal N double exposure;
(3) Means for selecting a pixel part to be used so that an area of an overexposed area is minimized and an underexposed area does not occur with respect to an ideal N double exposure, and (4) an ideal From <6>, which is one of means for selecting a used pixel portion so that an area of an underexposed region is minimized and an overexposed region is not generated with respect to a typical N double exposure. <11> A method for producing a color filter according to <11>.
<13> In the connecting region between the heads, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads,
(1) With respect to the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connection region, the total area of the overexposed region and the underexposed region is minimized. Means for identifying a used pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
(2) Involvement in the exposure of the head-to-head connecting region so that the number of pixel units in the overexposed region and the number of pixel units in the underexposed region are equal to the ideal N-double exposure. Means for identifying an unused pixel part from the pixel part to be selected, and selecting the pixel part excluding the unused pixel part as a used pixel part;
(3) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the overexposed region is minimized and the underexposed region is not generated. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part; and
(4) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the underexposed region is minimized and the region that is overexposed is not generated. , Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
The method for producing a color filter according to any one of <6> to <12>.
<14> The color filter manufacturing method according to <13>, wherein the unused pixel parts are specified in units of rows.

<15> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel elements, N (n−1) pixel element columns for N multiple exposures The method for producing a color filter according to any one of <5> to <14>, wherein the reference exposure is performed using only the image element part constituting the above. In the method for producing a color filter according to <15>, in order to specify a used pixel part in the used pixel part specifying unit, among the usable pixel parts, (N-1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
<16> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, a pixel part row is formed every 1 / N lines for N of N double exposures. The method for producing a color filter according to any one of <5> to <14>, wherein the reference exposure is performed using only the picture element portion. In the method for producing a color filter according to <16>, in order to specify a used pixel part in the used pixel part specifying unit, among N of the usable pixel elements, Reference exposure is performed using only the pixel part constituting the pixel part column for each 1 / N row, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<17> The <1> to <16>, wherein the used pixel part specifying means includes a slit and a photodetector as a light spot position detecting means and an arithmetic unit connected to the photodetector as a pixel part selecting means. The method for producing a color filter according to any one of the above.
<18> The method for producing a color filter according to any one of <1> to <17>, wherein N in N-exposure exposure is a natural number of 3 or more and 7 or less.

<19> The light modulation means further includes pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. The method for producing a color filter according to any one of <1> to <18>, wherein the color filter is modulated according to the method.
<20> From <1> to <1> further including conversion means for converting the pattern information so that a dimension of a predetermined part of the pattern represented by the pattern information matches a dimension of a corresponding part that can be realized by the designated used pixel part. 19> The method for producing a color filter according to any one of the above.

<21> The method for producing a color filter according to any one of <1> to <20>, wherein the light modulator is a spatial light modulator.
<22> The method for producing a color filter according to <21>, wherein the spatial light modulator is a digital micromirror device (DMD).
<23> The color filter manufacturing method according to any one of <21> to <22>, wherein the picture element portion is a micromirror.

<24> The method for producing a color filter according to any one of <1> to <23>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the method for producing a color filter according to <24>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, after that, the photosensitive layer is developed to form an extremely fine pattern.
<25> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects the laser beams irradiated from the plurality of lasers and converges them on the incident end face of the multimode optical fiber; The method for producing a color filter according to any one of <1> to <24>. In the method for manufacturing a color filter according to <25>, the light irradiation unit condenses the laser beams irradiated from the plurality of lasers by the collective optical system, and the incident end surface of the multimode optical fiber. By converging, the exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. For example, after that, the photosensitive layer is developed to form an extremely fine pattern.

<26> The method for producing a color filter according to any one of <1> to <25>, wherein the photosensitive layer is formed by applying a photosensitive composition to a surface of a substrate and drying.
<27> A photosensitive transfer material obtained by laminating a photosensitive composition on a support, and a laminate on the substrate such that the surface opposite to the support and the substrate are in contact with each other. Then, the method for producing a color filter according to any one of <1> to <26>, wherein the color filter is formed by peeling off the support.
<28> The method for producing a color filter according to any one of <1> to <27>, wherein the photosensitive composition is colored at least black (K).
<29> Using a photosensitive composition colored in at least three primary colors of red (R), green (G), and blue (B), R, G, and B in a predetermined arrangement on the surface of the substrate The method for producing a color filter according to any one of <1> to <28>, wherein the color filter is formed by sequentially repeating the photosensitive layer forming step, the exposure step, and the development step for each of the colors.
<30> At least pigment C.I. I. Pigment Red 254 is colored green (G) with pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 139 and at least a pigment C.I. I. It is a manufacturing method of the color filter as described in said <29> using pigment blue 15: 6.
<31> Pigment C.I. I. Pigment red 254 and pigment C.I. I. Pigment Red 177 at least one pigment is changed to a green (G) coloring pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 150 pigment, and blue (B) pigment C.I. I. Pigment blue 15: 6 and pigment C.I. I. The method for producing a color filter according to <29>, wherein at least one pigment of pigment violet 23 is used.

<32> A color filter manufactured by the method for manufacturing a color filter according to any one of <1> to <31>.
<33> A display device using the color filter according to <33>.

  According to the present invention, it is possible to solve the conventional problems, and without using a photomask, a shift in the mounting position and mounting angle of the exposure head, and between the pixel portion and the exposure surface of the pattern forming material. Variation in the resolution of the pattern formed on the exposed surface of the photosensitive layer by leveling out the effects of variations in exposure due to various aberrations of the optical system and pattern distortion caused by distortion of the picture element itself By reducing unevenness in density and density, the line width of black images is extremely small, high-definition can be formed, low cost, excellent display characteristics, portable terminals, portable game machines, notebook computers, TV monitors, etc. Manufacturing method of color filter suitably used for liquid crystal display device (LCD), PALC (plasma addressed liquid crystal), plasma display, etc., Excellent color filter display characteristics produced by the production method of the fine the color filter, and it is possible to provide a display device using the color filter. Further, according to the present invention, unevenness (coating unevenness and display unevenness) observed after development can be reduced.

(Color filter manufacturing method)
The method for producing a color filter of the present invention includes at least a photosensitive layer forming step, an exposure step, and a development step, and further includes other steps appropriately selected as necessary.
The color filter of the present invention is manufactured by the method for manufacturing the color filter of the present invention.
The display device of the present invention uses the color filter of the present invention, and further includes other means as necessary.
Hereinafter, details of the color filter and the display device of the present invention will be clarified through the description of the method of manufacturing the color filter of the present invention.

[Photosensitive layer forming step]
The photosensitive layer forming step is a step of forming at least the photosensitive layer on the surface of the substrate using the photosensitive composition containing a binder, a polymerizable compound, a colorant, and a photopolymerization initiator, Further, it is a step of forming other layers appropriately selected.

The method for forming the photosensitive layer and other layers is not particularly limited and may be appropriately selected depending on the intended purpose. By performing either, a method of forming by laminating, a combination thereof, and the like can be mentioned.
Suitable examples of the photosensitive layer forming step include the photosensitive layer forming step of the first aspect and the photosensitive layer forming step of the second aspect described below.

  As the photosensitive layer forming step of the first aspect, at least a photosensitive layer is formed on the surface of the substrate by applying the photosensitive composition to the surface of the substrate and drying, and further appropriately selected. And a step of forming other layers.

  In the photosensitive layer forming step of the second aspect, a photosensitive transfer material formed by forming a photosensitive transfer layer comprising the photosensitive composition into a film is used, and the photosensitive transfer layer is applied to a substrate. A step of forming at least a photosensitive layer on the surface of the substrate by laminating under at least one of heating and pressurization so as to come into contact with each other, and further forming other appropriately selected layers may be mentioned.

  In the photosensitive layer forming step of the first aspect, the method for applying and drying the photosensitive composition is not particularly limited and can be appropriately selected according to the purpose. For example, on the surface of the substrate, Examples include a method in which the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive composition solution, and the solution is directly applied and dried for lamination.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably.

The coating method is not particularly limited and can be appropriately selected depending on the purpose. For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. The method of apply | coating is mentioned. In this invention, it is preferable to carry out by the coating device (slit coater) using the slit-shaped nozzle which has a slit-shaped hole in the part which discharges a liquid. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Application Laid-Open No. 2001-310147 and the like are preferably used.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, According to the objective, it can select suitably, 0.5-10 micrometers is preferable, 0.75-6 micrometers is more preferable, and 1-3 micrometers is especially preferable.

Other layers formed in the photosensitive layer forming step of the first aspect are not particularly limited and can be appropriately selected depending on the purpose. For example, an oxygen blocking layer, a release layer, an adhesive layer, a light absorbing layer And a surface protective layer.
There is no restriction | limiting in particular as a formation method of the said other layer, According to the objective, it can select suitably, For example, the method of apply | coating on the said photosensitive layer, The method of laminating | stacking the other layer formed in the sheet form Etc.

In the photosensitive layer forming step of the second aspect, as a method of forming a photosensitive layer on the surface of the base material and other layers appropriately selected as necessary, a support and The photosensitive transfer material (photosensitive film) having a photosensitive layer obtained by laminating a photosensitive composition on a support and other layers appropriately selected as necessary, is heated and pressurized at least either Specifically, the photosensitive layer having a photosensitive transfer layer (hereinafter sometimes simply referred to as “photosensitive layer”) made of the photosensitive composition on the support. Preferably, the photosensitive transfer material is laminated so that the photosensitive transfer layer (photosensitive layer) is on the surface side of the substrate, and then the support is peeled off from the photosensitive transfer layer (photosensitive layer). Can be mentioned.
By peeling off the support, it is possible to prevent a blurred image from being formed on the image formed on the photosensitive layer due to light scattering or refraction by the support, and to obtain a predetermined pattern with high resolution. .
In addition, when the said photosensitive transfer material has a protective film mentioned later, this protective film is peeled and it laminates | stacks so that the said photosensitive layer may overlap with the said base material.

There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 70-130 degreeC is preferable and 80-110 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, a heat press, a heat roll laminator (for example, Hitachi Industries, Ltd.) , Lamic II type), vacuum laminator (for example, MVLP500 manufactured by Meiki Seisakusho) and the like are preferable.

  The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer can be peeled off and that light transmittance is good, and that the surface is smooth. Is more preferable.

  There is no restriction | limiting in particular as thickness of the said support body, According to the objective, it can select suitably, For example, 4-300 micrometers is preferable, 5-175 micrometers is more preferable, and 10-100 micrometers is especially preferable.

  There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular as the length of the said elongate support body, For example, the thing of length 10m-20000m is mentioned.

The support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytri Various plastic films such as fluoroethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

  Formation of the photosensitive layer in the photosensitive transfer material can be performed by the same method as the application and drying of the photosensitive composition solution to the substrate (the photosensitive layer forming method of the first aspect).

The protective film is a film having a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as thickness of the said protective film, According to the objective, it can select suitably, For example, 5-100 micrometers is preferable, 8-50 micrometers is more preferable, 10-40 micrometers is especially preferable.

  There is no restriction | limiting in particular as a location provided in the said photosensitive transfer material of the said protective film, Although it can select suitably according to the objective, Usually, it provides on the said photosensitive layer.

  When the protective film is used, the relationship between the adhesive force A of the photosensitive layer and the support and the adhesive force B of the photosensitive layer and the protective film is preferably adhesive force A> adhesive force B. .

The coefficient of static friction between the support and the protective film is preferably 0.3 to 1.4, and more preferably 0.5 to 1.2.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

The protective film is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those used for the support, silicone paper, polyethylene, polypropylene laminated paper, polyolefin or polytetrafluoro. An ethylene sheet etc. are mentioned, Among these, a polyethylene film, a polypropylene film, etc. are mentioned as a particularly preferable thing.
Examples of the combination of the support and the protective film (support / protective film) include a combination described in paragraph No. 0151 of JP-A-2005-70767, a combination of polyethylene terephthalate / polyethylene terephthalate, and the like.

  As the protective film, in order to satisfy the above-described relationship of adhesive strength, it is preferable to perform surface treatment to adjust the adhesion between the protective film and the photosensitive layer. For example, as a method of the surface treatment, Examples include the method described in paragraph No. 0151 of JP-A-2005-70767.

  There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, a thermoplastic resin layer, an intermediate | middle layer, etc. are mentioned.

-Thermoplastic resin layer-
The thermoplastic resin layer (hereinafter sometimes referred to as “cushion layer”) enables alkali development, and the transferred material is contaminated by the alkali-soluble thermoplastic resin layer that protrudes during transfer. It is preferable that it is soluble in alkali from the viewpoint of preventing the occurrence of transfer defects, and when transferring the photosensitive transfer material onto the transfer target, transfer defects caused by unevenness present on the transfer target are effective. It is preferable that the photosensitive transfer material has a function as a cushioning material, and can be deformed according to the unevenness present on the transferred material when the photosensitive transfer material is heated and adhered onto the transferred material. More preferably.

As a material used for the thermoplastic resin layer, for example, an organic polymer substance described in JP-A-5-72724 is preferable, and the Viker Vicat method (specifically, American Materials Testing Method ASTM D1235) is used. It is particularly preferred that the softening point by the polymer softening point measurement method according to (1) is selected from organic polymer substances having a temperature of about 80 ° C. or lower. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylate esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate or saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxymethylated sodium Ron, and organic polymers of the polyamide resins, such as N- dimethylamino nylon and the like.
The dry thickness of the thermoplastic resin layer is preferably 2 to 30 μm, more preferably 5 to 20 μm, and particularly preferably 7 to 16 μm.

-Intermediate layer-
The intermediate layer is provided on the photosensitive layer, and provided between the photosensitive layer and the alkali-soluble thermoplastic resin layer when the photosensitive transfer material has an alkali-soluble thermoplastic resin layer. It is done. Since an organic solvent is used in the formation of the photosensitive layer and the alkali-soluble thermoplastic resin layer, when the intermediate layer is located between them, the two layers can be prevented from mixing with each other.

The intermediate layer is preferably one that is dispersed or dissolved in water or an aqueous alkali solution.
As the material for the intermediate layer, known materials can be used. For example, polyvinyl ether / maleic anhydride polymer, carboxyalkyl described in JP-A No. 46-2121 and JP-B No. 56-40824 Water-soluble salt of cellulose, water-soluble cellulose ether, water-soluble salt of carboxyalkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, water-soluble polyamide, water-soluble salt of polyacrylic acid, gelatin, ethylene oxide polymer, various Water soluble salts of the group consisting of starch and the like, styrene / maleic acid copolymers, maleate resins, and the like.
These may be used alone or in combination of two or more. Among these, it is preferable to use a hydrophilic polymer, and among these hydrophilic polymers, it is preferable to use at least polyvinyl alcohol, and a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

There is no restriction | limiting in particular as said polyvinyl alcohol, Although it can select suitably according to the objective, The saponification rate has preferable 80% or more.
When using the said polyvinyl pyrrolidone, as content, 1-75 volume% is preferable with respect to solid content of this intermediate | middle layer, 1-60 volume% is more preferable, 10-50 volume% is especially preferable.
When the content is less than 1% by volume, sufficient adhesion to the photosensitive layer may not be obtained. On the other hand, when the content exceeds 75% by volume, the oxygen-blocking ability may be decreased. Absent.

  The intermediate layer preferably has a low oxygen permeability. When the oxygen permeability of the intermediate layer is large and the oxygen blocking ability is low, it may be necessary to increase the amount of light at the time of exposure to the photosensitive layer, or it may be necessary to lengthen the exposure time, and the resolution also decreases. May end up.

There is no restriction | limiting in particular as thickness of the said intermediate | middle layer, According to the objective, it can select suitably, It is preferable that it is about 0.1-5 micrometers, and 0.5-2 micrometers is more preferable.
If the thickness is less than 0.1 μm, the oxygen permeability may be too high, and if it exceeds 5 μm, it takes a long time for development or removal of the intermediate layer, which is not preferable.

  The structure of the photosensitive transfer material is not particularly limited and may be appropriately selected depending on the purpose.For example, on the support, on the temporary support, a thermoplastic resin layer, an intermediate layer, The form etc. which have a photosensitive layer in this order are mentioned. The photosensitive layer may be a single layer or a plurality of layers.

  The photosensitive transfer material is preferably stored, for example, wound around a cylindrical core, wound in a long roll shape. There is no restriction | limiting in particular as the length of the said elongate photosensitive transfer material, For example, it can select suitably from the range of 10m-20,000m. In addition, slitting may be performed so that the user can easily use, and a long body in a range of 100 m to 1,000 m may be formed into a roll shape. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit in the said roll-shaped photosensitive transfer material sheet form. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and containing a desiccant) on the end face, and use a low moisture-permeable material for packaging. Is preferred.

  The photosensitive transfer material can be widely used for pattern formation of display members such as color filters, pillars, ribs, spacers, partition walls, etc. Among them, suitable for the method for producing a color filter of the present invention. Can be used.

  In addition, there is no restriction | limiting in particular as an exposure method to the laminated body which has the photosensitive layer formed by the photosensitive layer forming method of the said 2nd aspect, According to the objective, it can select suitably, For example, the said photosensitive layer In the case where a film-like photosensitive transfer material is laminated on a support via a cushion layer, the support and, if necessary, the cushion layer are also peeled off, and then the intermediate layer (oxygen barrier layer) is interposed. It is preferable to expose the photosensitive layer.

<Photosensitive layer>
The photosensitive layer (color resist layer) formed in the photosensitive layer forming step includes at least a binder, a colorant, a polymerizable compound, and a photopolymerization initiator, and further includes other components appropriately selected as necessary. It is formed using the photosensitive composition containing.

<< Binder >>
For example, the binder is preferably swellable in an alkaline aqueous solution, and more preferably soluble in an alkaline aqueous solution.
As the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably exemplified.

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, Among these, a carboxyl group is preferable.
Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, and a modified epoxy resin. Among these, the solubility in a coating solvent, the solubility in an alkali developer, and the like. From the viewpoints of solubility, suitability for synthesis, ease of preparation of film properties, etc., a vinyl copolymer having a carboxyl group is preferred.

  The vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono Examples include (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  The other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid diesters. , Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, Vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, phosphoric acid mono (2-acryloyloxyethyl ester), phosphorus Acid mono (1- Chill-2-acryloyloxyethyl ester), functional groups (e.g., a urethane group, an urea group, a sulfonamide group, a phenol group and a vinyl monomer and the like having an imide group).

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) Acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate , Polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, Nylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butyl acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like.

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic. Preferable examples include 2-ethylhexyl acid, styrene, chlorostyrene, bromostyrene, and hydroxystyrene.

  The said other copolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

  The vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.

  The suitable solvent used in the solution polymerization method is not particularly limited and may be appropriately selected depending on the monomer used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, Examples include isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. These solvents may be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile). Examples thereof include peroxides such as azo compounds and benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

There is no restriction | limiting in particular as content rate of the polymeric compound which has a carboxyl group in the said vinyl copolymer, Although it can select suitably according to the objective, For example, 5-50 mol% is preferable, 10-40 mol % Is more preferable, and 15 to 35 mol% is particularly preferable.
If the content is less than 5 mol%, developability to alkaline water may be insufficient, and if it exceeds 50 mol%, the developer resistance of the cured portion (pixel portion, image portion) may be insufficient. There is.

There is no restriction | limiting in particular as molecular weight of the binder which has the said carboxyl group, Although it can select suitably according to the objective, For example, 2,000-300,000 are preferable as a weight average molecular weight, 4,000-150 000 is more preferable.
When the weight average molecular weight is less than 2,000, the strength of the film tends to be insufficient and stable production may be difficult, and when it exceeds 300,000, developability may be deteriorated.

  The binder which has the said carboxyl group may be used individually by 1 type, and may use 2 or more types together. When two or more binders are used in combination, for example, a combination of two or more binders composed of different copolymerization components, two or more binders having different weight average molecular weights, two or more binders having different degrees of dispersion, etc. Is mentioned.

  The binder having a carboxyl group may be partially or entirely neutralized with a basic substance. The binder may be used in combination with resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.

  Moreover, as the binder, a resin soluble in an alkaline aqueous solution described in Japanese Patent No. 2873889 can be used.

There is no restriction | limiting in particular as content of the said binder in the said photosensitive layer, Although it can select suitably according to the objective, For example, 5-80 mass% is preferable, 10-70 mass% is more preferable, 15-15 50% by mass is particularly preferred.
When the content is less than 5% by mass, the alkali developability may be lowered, and when it exceeds 80% by mass, the stability with respect to the development time may be lowered. The content may be the total content of the binder and the polymer binder used in combination as necessary.

The acid value of the binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 70 to 250 mgKOH / g, more preferably 90 to 200 mgKOH / g, and 100 to 180 mgKOH / g. Particularly preferred.
When the acid value is less than 70 mgKOH / g, the developability may be insufficient or the resolution may be inferior, and the pattern may not be obtained with high definition. At least one of the liquidity and the adhesiveness may deteriorate, and the pattern may not be obtained with high definition.

<< polymerizable compound >>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. However, the polymerizable compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. A compound is preferable, for example, at least 1 sort (s) selected from the monomer which has a (meth) acryl group is mentioned suitably.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.

10-60 mass% is preferable, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 15-50 mass% is more preferable, and 20-40 mass% is especially preferable. When the solid content is less than 10% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and when it exceeds 60% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.
The ratio of the polymerizable compound and the binder is a mass ratio, preferably polymerizable compound / binder = 0.5 to 1.5, more preferably 0.6 to 1.2, and 0.65 to 1.1. Particularly preferred. If this range is exceeded, problems such as residues may occur during development, and if it is less than this range, the durability of the completed color filter may be reduced.

<< photopolymerization initiator >>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is visible from the ultraviolet region. It is preferable to have photosensitivity to the light, and it may be an activator that produces some kind of action with a photoexcited sensitizer and generates an active radical. Initiator may be used.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), phosphine oxide, hexaarylbiimidazole, oxime derivatives, organic peroxides, Examples include thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, and the like.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724 , F. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, and U.S. Pat. No. 4,221,976. Compounds described in the specification, and the like.

  Further, the vicinal polyketaldonyl compound described in US Pat. No. 2,367,660, the acyloin ether compound described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512 Aromatic acyloin compounds substituted with α-hydrocarbons described above, polynuclear quinone compounds described in US Pat. No. 3,046,127 and US Pat. No. 2,951,758, JP-A-2002-229194 Organic boron compounds, radical generators, triarylsulfonium salts (for example, salts with hexafluoroantimony and hexafluorophosphate), phosphonium salt compounds (for example, (phenylthiophenyl) diphenylsulfonium salts, etc.) (cationic polymerization initiators) Effective), International 01 / Such as onium salt compounds described in 1428 pamphlet can be mentioned.

  Wakabayashi et al., Bull. Chem. Soc. As a compound described in Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl)- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2, 4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-n-nonyl-4,6- Bis (trichloromethyl) 1,3,5-triazine, and 2-(alpha, alpha, beta-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

Examples of the compound described in the British Patent No. 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4. , 6-Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy) Styryl) -4-amino-6-trichloromethyl-1,3,5-triazine and the like.
Examples of the compound described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

  Examples of the compound described in German Patent No. 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -(4-methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloro Methyl) -1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan -2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine and the like.

  F. above. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964) include, for example, 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (tribromomethyl); -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl) -1,3,5- Examples include triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

  Examples of the compound described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Naphtyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropyl) Phenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloro Chill) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-281728 include 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2 , 6-Difluorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

  Examples of the compounds described in JP-A-5-34920 include 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl]-. 1,3,5-triazine, trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4 -Chlorophenyl) -4,6-bis (tribromomethyl) -s-triazine and the like.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl)- 1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1 3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4 -Oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromemethyl-5-styryl-1,3,4-oxadiazole Etc.).

  Examples of the oxime derivative suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

  Further, as photopolymerization initiators other than the above, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and the like, polyhalogen compounds (for example, Carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbonylbi (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206 , Coumarin compounds described in JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate) Acid n-butyl, 4-dimethylaminobenzoic acid phenetic acid 4-dimethylimidobenzoic acid 2-phthalimidoethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4- Dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl- 4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecyl Amines, aminofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc.), acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6- Difluoro 3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), JP-A-53-133428 Gazette, Japanese Patent Publication No.57-1819 No. 57-6096, and US Pat. No. 3,615,455, and the like.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

  Examples of the hexaarylbiimidazole compound include 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-bisimidazole, 2,2′-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4 -Phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6- Lichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5 '-Tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-cyanophenyl) -4,4', 5.5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2 '-Bis (2-cyanophenyl) -4,4', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5 , 5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-e Xoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2- Ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis ( 4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis ( 2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenylphenyl) Enyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4 -Phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetra Phenylbiimi Sol, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-cyanophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis ( 2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetra Phenylbiimidazole, 2,2′-bis (2,4-dimethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diethylphenyl) -4,4 ′ , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis ( 2-phenylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diphenylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2,2′-bis (2,4,6-triphenylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and the like.

As content of the said photoinitiator, 0.1-50 mass% is preferable with respect to the total solid component in the said photosensitive composition, 0.5-30 mass% is more preferable, 1-20 mass% Is particularly preferred.
When the content of the photopolymerization initiator is expressed by a mass ratio with the polymerizable compound, the photopolymerization initiator / polymerizable compound is preferably 0.01 to 0.2, more preferably 0.02 to 0.1. Preferably, 0.03 to 0.08 is particularly preferable. If it exceeds this range, there is a problem that a development residue or a precipitation failure occurs. If it is less than this range, sufficient sensitivity may not be obtained.

In addition to the photopolymerization initiator, a sensitizer can be added for the purpose of adjusting exposure sensitivity and photosensitive wavelength in exposure to the photosensitive layer described later.
The sensitizer can be appropriately selected by visible light, ultraviolet light, visible light laser, or the like as a light irradiation means described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers according to the purpose. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), Xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines ( For example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), squariums (for example, squalium), acridones (for example, acridone) Chloroacridone, N-methylacridone, N-butylacridone, 10-N-butyl-2-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7- Diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2 -Furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7 Examples thereof include diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5, 7-dipropoxycoumarin, and others, as well as JP-A-5-19475 and JP-A-7-271028. And JP-A 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, and the like.

  Examples of the combination of the photopolymerization initiator and the sensitizer include, for example, an electron transfer start system described in JP-A-2001-305734 [(1) an electron donating initiator and a sensitizing dye, (2) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.

  As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components in the said photosensitive composition, 0.1-20 mass% is more preferable, 0.2-10 mass% Is particularly preferred. When the content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and productivity may be reduced. The sensitizer may be precipitated from the photosensitive layer.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
Particularly preferred examples of the photopolymerization initiator include halogenated carbonization having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton, which can handle laser light having a wavelength of 405 nm in the later-described exposure. Examples include a composite photoinitiator in which a hydrogen compound and an amine compound as a sensitizer are combined, a hexaarylbiimidazole compound, or titanocene.

<< Colorant >>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, an organic pigment, an inorganic pigment, dye, etc. are mentioned.
Any one selected from dendritic branched molecules in which metal ions are coordinated as a coloring agent and dendritic branched molecules containing at least one metal particle of metal particles and alloy particles, separately or in combination with these colorants It is also possible to contain the following dendritic molecules.

  Examples of the colorant include a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, and a black pigment. In the case of forming a color filter, the photosensitive composition is Since a plurality of colored compositions colored in three primary colors (B, G, R) and black (K) are used, a pigment such as a blue pigment, a green pigment, a red pigment, and a black pigment is preferably used. .

  Examples of the pigment include a coloring material described in paragraph Nos. 0038 to 0040 of JP-A No. 2005-17716, a pigment described in paragraph Nos. 0068 to 0072 of JP-A No. 2005-361447, and JP-A No. 2005-17521. Preferable examples include coloring agents described in paragraph numbers 0080 to 0088 of the publication.

  In addition, the said coloring agent may be used individually by 1 type, or can also be used in combination of 2 or more type.

  In the color filter of the present invention, the combination of the colorants for effectively realizing good display characteristics (darker color) in both the transmission mode and the reflection mode in a device such as a portable terminal or a portable game machine. (I) In the photosensitive composition of R, the pigment C.I. I. Pigment Red 254, and (ii) the pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 139 is used in combination, and in the photosensitive composition of (iii) B, pigment C.I. I. Pigment Blue 15: 6 is preferably used.

Here, the C.I. I. The content of Pigment Red 254 is preferably 0.274 to 0.335 g / m ² when the photosensitive composition is applied with a dry film thickness of 1 to 3 μm, and is preferably 0.280 to 0.329 g / m ^2. m ² is more preferable, and 0.290 to 0.320 g / m ² is particularly preferable.
C. in said (ii). I. The content of Pigment Green 36 is preferably 0.355 to 0.437 g / m ² when the photosensitive composition is applied with a dry film thickness of 1 to 3 μm, and 0.364 to 0.428 g / m ^2. m ² is more preferable, and 0.376 to 0.412 g / m ² is particularly preferable.
C. in said (ii). I. The content of CI Pigment Yellow 139 is preferably 0.052~0.078g / ^{m 2,} more preferably from 0.060~0.070g / ^{m 2,} 0.062~0.068g / ^{m 2} is particularly preferred. In (ii), C.I. I. Pigment green 36 / C.I. I. The pigment yellow 139 ratio is preferably 5.4 to 6.7, more preferably 5.6 to 6.6, and particularly preferably 5.8 to 6.4.
C. in (iii) above. I. The content of Pigment Blue 15: 6 is preferably 0.28 to 0.38 g / m ² when the photosensitive composition is applied with a dry film thickness of 1 to 3 μm, and preferably 0.29 to 0.36 g. / more preferably ^m is ^2, and particularly preferably 0.30～0.34G / ^{m 2.}

  In addition, the color filter of the present invention realizes high display characteristics (wide color reproduction range and high color temperature) when used in a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor. Examples of the combination of the colorants include (I) the pigment C.I. in the red (R) photosensitive composition. I. Pigment red 254 and C.I. I. Pigment Red 177 is used, and in the photosensitive composition of (II) green (G), pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 150 is used in combination, and in the photosensitive composition of (III) blue (B), pigment C.I. I. Pigment blue 15: 6 and C.I. I. Pigment violet 23 is preferably used in combination.

Here, the C.I. I. The content of Pigment Red 254 is preferably 0.6 to 1.1 g / m ² when the photosensitive composition is applied with a dry film thickness of 1 to 3 μm, and 0.80 to 0.96 g / m ^2. m ² is more preferable, and 0.82 to 0.94 g / m ² is particularly preferable.
C. in (I) above. I. The content of Pigment Red 177 is preferably 0.10 to 0.30 g / m ² when the photosensitive composition is applied with a dry film thickness of 1 to 3 μm, and is preferably 0.20 to 0.24 g / m ^2. m ² is more preferable, and 0.21 to 0.23 g / m ² is particularly preferable.
C. in said (II). I. The content of Pigment Green 36 is preferably 0.80 to 1.45 g / m ² when the photosensitive composition is applied with a dry film thickness of 1 to 3 μm, and preferably 0.90 to 1.34 g / m ^2. m ² is more preferable, and 0.95 to 1.29 g / m ² is particularly preferable.
C. in said (II). I. The content of pigment yellow 150 is preferably 0.30~0.65g / ^{m 2,} and more preferably 0.38~0.58g / ^{m 2.} In (II), C.I. I. Pigment green 36 / C.I. I. The pigment yellow 150 ratio is preferably 0.40 to 0.50.
C. in said (III). I. The content of Pigment Blue 15: 6 is preferably 0.50 to 0.75 g / m ² when the photosensitive composition is applied with a dry film thickness of 1 to 3 μm, and is preferably 0.59 to 0.8. It is more preferably 67 g / m ² , and particularly preferably 0.60 to 0.66 g / m ² .
C. in said (III). I. The content of Pigment Violet 23 is preferably 0.03 to 0.10 g / m ² when the photosensitive composition is applied with a dry film thickness of 1 to 3 μm, and preferably 0.06 to 0.08 g / m. ² is more preferable, and 0.066 to 0.074 g / m ² is particularly preferable. In (III), C.I. I. Pigment Blue 15: 6 / C.I. I. It is preferable that the pigment violet 23 ratio is 12-50.

When the colorant as described above is used, the particle size of the pigment or dye is preferably 1 nm to 10 ⁴ nm, more preferably 10 to 80 nm, and particularly preferably 20 to 70 nm. Preferably, it is 30 nm-60 nm. Since the photosensitive layer is a thin layer, when the particle size of the pigment or the like is not in the above range, it cannot be uniformly dispersed in the resin layer, and it is difficult to produce a high-quality color filter. Therefore, it is not preferable.

<< Other ingredients >>
In the said photosensitive composition, you may contain components, such as a plasticizer, surfactant, a ultraviolet absorber, a thermal polymerization inhibitor, as another component, for example.

The plasticizer may be added to control film physical properties (flexibility) of the photosensitive layer.
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, and the like. Phthalic acid esters: Triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters of tricresyl phosphate, triphenyl phosphate, etc. Acid esters; Amides such as 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl Aliphatic dibasic acid esters such as sepacate, dioctyl azelate, dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid Examples include glycols such as dioctyl acid, polyethylene glycol, and polypropylene glycol.

  As content of the said plasticizer, 0.1-50 mass% is preferable with respect to all the components of the said photosensitive layer, 0.5-40 mass% is more preferable, 1-30 mass% is especially preferable.

The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the surfactant is appropriately selected from an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like. You can choose.
Further, as the surfactant, the following formula (1)
^{_{C 8 F 17 SO 2 N (}} R 1) CH 2 CH 2 O (CH 2 CH 2 O n R 2) ··· (1)
Fluorosurfactants represented by the formula are preferred.
However, in the formula, ^{R 1} and ^{R 2} each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 2 to 30.
Examples of R ¹ include a methyl group, an ethyl group, and an isopropyl group, and examples of R ² include a hydrogen atom.
As said n, 10-25 are preferable and 10-20 are more preferable.
As specific examples of the surfactant represented by the above formula, Megafac F-141 (n = 5), F-142 (n = 10), F = 143 (n = 15), F-144 (n = 20) (Brand name: Dainippon Ink & Chemicals, Inc.).

Furthermore, as the surfactant, surfactants represented by the following formulas (2) to (5) are preferably exemplified.
_{Rf1-X- (CH 2 CH 2} O) n R 1 ··· (2)
Rf1-X- (CH ₂ CH ₂ O) _n R ² (3)
_{Rf1-X- (CH 2 CH 2} O) n (CH 2 CH 2 CH 2 O) m R 1 ··· (4)
_{Rf1-X- (CH 2 CH 2} O) n (CH 2 CH 2 CH 2 O) m Rf2 ··· (5)

In the formula (2) ~ (5), R 1 and ^{R 2} are Tansomoto 18, preferably 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group include a saturated alkyl group and an unsaturated alkyl group.
Examples of the structure of the alkyl group include those having a linear structure and a branched structure, and among these, those having a branched structure are preferably exemplified.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, otatadecyl group , Eicosanyl group, docosanyl group, 2-chloroethyl group, 2-promoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-promopropyl group and the like. These alkyl groups may be substituted with a halogen atom, an acyl group, an amino group, a cyano group, an alkyl group, an alkoxy group, an aryl group which may be substituted with alkyl or haloalkyl, an amide group, or the like.
In the formulas (2) to (5), Rf1 and Rf2 each independently represent a perfluoro group having 1 to 18, preferably 2 to 12, more preferably 4 to 10 carbon atoms.
Examples of the perfluoro group include a saturated perfluoro group and an unsaturated perfluoro group.
Examples of the structure of the perfluoro group include those having a linear structure and a branched structure. Among these, those having a branched structure are preferably exemplified, and at least one of Rf1 and Rf2 has a branched structure. A thing is mentioned more suitably.
Examples of the perfluoro group include perfluorononenyl, perfluoromethyl, perfluoropropylene, perfluorononinel, perfluorobenzoic acid, perfluoropropylene, perfluoropropyl, perfluoro (9-methyloctyl), perfluoro Fluoromethyloctyl, perfluorobutyl, perfluoro-3-methylbutyl, perfluorohexyl, perfluorooctyl, perfluoro 7-octylethyl, fluoroheptyl, perfluorodecyl, perfluorobutyl and the like can be mentioned. These perfluoro groups may be substituted with a halogen atom, acyl group, amino group, cyano group, alkyl group, alkoxy group, alkyl or haloalkyl, or may be substituted with an aryl group, an amide group, or the like. Good.
Rf1 and Rf2 may be the same as or different from each other.
In said Formula (2)-(5), n represents the integer of 1-40, Preferably the integer of 4-25 is represented.
In said Formula (2)-(5), m represents the integer of 0-40, Preferably the integer of 0-25 is represented.
In the formula (2) ~ (5), -X- _{is, - (CH 2) l -} (l 1 to 10, preferably represents an integer of 1 to 5), - CO-O -, - O -, -NHCO-, or -NHCOO- is represented.
The surfactants represented by the formulas (2) to (5) can be used alone or in combination of two or more.

As content of the said surfactant, 0.001-10 mass% is preferable with respect to solid content of the photosensitive composition.
When the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be deteriorated.

  When the photosensitive composition contains the surfactant, the fluidity as a coating liquid is improved, and the adhesion of the liquid in the nozzles and pipes and containers of spin coaters and slit coaters used in the coating process. Since the residue remaining as dirt in the nozzle can be effectively reduced, the amount of cleaning liquid and the work time required for cleaning when changing the coating liquid can be reduced, and the productivity of the color filter can be improved. Can do. In addition, it is possible to improve surface unevenness that occurs when the color resist layer is formed.

The thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2′-methylenebis (4-methyl- 6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, etc. It is done.
As content of the said thermal-polymerization inhibitor, 0.0001-10 mass% is preferable with respect to all the components of a photosensitive composition, 0.0005-5 mass% is more preferable, 0.001-1 mass% is Particularly preferred.

Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-di-phenyl acrylate, 2,2'-hydroxy-4- Methoxybenzophenone, nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethol-4-pyridine) -seba 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4 -Piperenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5 Triazin-2-yl] amino} -3-phenylcoumarin and the like.
In addition, 0.5-15 mass% is preferable, as for content of the ultraviolet absorber with respect to the total solid of a photosensitive composition, 1-12 mass% is more preferable, and 1.2-10 mass% is especially preferable.

The photosensitive composition for forming the photosensitive layer can be prepared using a solvent.
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexane, ethyl carbitol acetate, butyl Preferred examples include carbitol acetate and propylene glycol methyl ether acetate. These solvents can be used alone or in combination of two or more.

  There is no restriction | limiting in particular as the addition amount of the said solvent at the time of preparation of the said photosensitive composition, Although it can select suitably according to the objective, The total solid content concentration of the said photosensitive composition is 5-80 mass%. It is preferable to add so that it may become, It is more preferable to add so that it may become 10-60 mass%, It is especially preferable to add so that it may become 15-50 mass%.

The thickness of the photosensitive layer is preferably 0.3 to 10 μm, more preferably 0.75 to 6 μm, and particularly preferably 1.0 to 3 μm.
If the layer thickness is less than 0.3 μm, pinholes are likely to occur when the coating solution for the photosensitive layer is applied, and the production suitability may be reduced. May take a long time.

<Base material>
The base material used in the photosensitive layer forming step is not particularly limited, and may be appropriately selected from known materials having high surface smoothness to those having an uneven surface according to the purpose. However, a plate-like substrate (substrate) is preferable. Specifically, a glass plate (for example, soda glass plate, glass plate sputtered with silicon oxide, non-alkali glass plate, quartz glass plate, etc.), synthetic resin property Film, paper, and metal plate.

  The base material can be used by forming a laminate formed by laminating the photosensitive layer so that the photosensitive layer in the photosensitive layer overlaps the base material. That is, by exposing the photosensitive layer of the laminate to the photosensitive layer, the exposed region can be cured, and a pattern can be formed by a development process described later.

[Exposure process]
The exposure step is an exposure head provided with a light irradiation means and a light modulation means for the photosensitive layer, and the column direction of the picture element portions is a predetermined set inclination angle with respect to the scanning direction of the exposure head. An exposure head arranged so as to form θ is used, and the exposure head is subjected to N multiple exposures (where N is a natural number of 2 or more) of the usable pixel parts by means of a used pixel part specifying means. The pixel part to be used is specified, and for the exposure head, the pixel part is specified by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in the exposure. And performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction.

In the present invention, “N double exposure” means that the exposed surface is irradiated with a straight line parallel to the scanning direction of the exposure head in almost all of the exposed region on the exposed surface of the photosensitive layer. This means exposure by setting that intersects N light spot rows (pixel rows). Here, the “light spot array (pixel array)” is a direction in which the angle formed with the scanning direction of the exposure head is smaller in the array of light spots (pixels) as pixel units generated by the pixel unit. Refers to a sequence of Note that the arrangement of the picture element portions is not necessarily a rectangular lattice shape, and may be, for example, an arrangement of parallelograms. Here, “substantially all areas” of the exposure area is described as a straight line parallel to the scanning direction of the exposure head by tilting the pixel part rows at both side edges of each picture element part. Since the number of drawing element rows of the used drawing element parts to be crossed decreases, even if it is used to connect a plurality of exposure heads in such a case, it is parallel to the scanning direction due to errors in the mounting angle and arrangement of the exposure heads. The number of pixel parts in the used pixel part that intersect with a straight line may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is only a fraction of the resolution. However, due to errors such as the mounting angle and the arrangement of the picture element parts, the pitch of the picture element parts along the direction orthogonal to the scanning direction does not exactly match the pitch of the picture element parts of other parts, and is parallel to the scanning direction. The number of used pixel parts that intersect with the straight line may increase or decrease within a range of ± 1. It is an order. In the following description, N multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”. Further, in the following description, “N multiple drawing” and “multiple exposure” are used as terms corresponding to “N double exposure” and “multiple exposure” for an embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method. The term “multiple drawing” shall be used.
N in the N-fold exposure is not particularly limited as long as it is a natural number of 2 or more, and can be appropriately selected according to the purpose. However, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .

In the exposure step, the exposure is preferably performed in a poor oxygen atmosphere, for example, in an inert gas atmosphere or in a state where an oxygen blocking layer is provided.
The exposure method in an oxygen-poor atmosphere is not particularly limited and may be appropriately selected depending on the intended purpose. A sample on which a photosensitive layer to be exposed is placed in an exposure space in a sample stage where an inert gas introduction hole is formed on at least one remaining side, and the inert gas introduction hole is inert from the inert gas introduction hole. For example, a method may be used in which exposure is performed while introducing a gas to cover the surface of the photosensitive layer with an inert gas.
In addition, it is possible to introduce an inert gas into the sealed space under reduced pressure using the exposure space as a sealed space.
The inert gas is not particularly limited as long as it can prevent the polymerization reaction of the photosensitive layer from being inhibited by the influence of oxygen, and can be appropriately selected according to the purpose. For example, nitrogen, helium, argon, etc. Is mentioned.

Hereinafter, an aspect of a method for producing a color filter of the present invention and an exposure apparatus suitably used for the method for producing the color filter will be described with reference to the drawings.
As said exposure apparatus, when the said base material is a glass substrate etc., a flat bed type exposure apparatus is mentioned suitably. When the base material is a flexible substrate or the like, an outer drum type exposure device, an inner drum type exposure device, or the like may be used. Hereinafter, a flat bed type exposure apparatus will be described.

<Exposure device>
As the exposure apparatus, as shown in FIG. 1, a flat plate shape that adsorbs and holds a laminated body (hereinafter referred to as “photosensitive material 12” or “photosensitive layer 12”) in which the photosensitive layers are laminated. The moving stage 14 is provided. Two guides 20 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 18 supported by the four legs 16. The stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable. The exposure apparatus 10 is provided with a stage driving device (not shown) that drives the stage 14 along the guide 20.

  A U-shaped gate 22 is provided at the center of the installation base 18 so as to straddle the movement path of the stage 14. Each end of the U-shaped gate 22 is fixed to both side surfaces of the installation base 18. A scanner 24 is provided on one side across the gate 22, and a plurality of (for example, two) sensors 26 that detect the front and rear ends of the photosensitive material 12 are provided on the other side. The scanner 24 and the sensor 26 are respectively attached to the gate 22 and fixedly arranged above the moving path of the stage 14. The scanner 24 and the sensor 26 are connected to a controller (not shown) that controls them.

  Here, for explanation, an X axis and a Y axis orthogonal to each other are defined in a plane parallel to the surface of the stage 14 as shown in FIG.

  A slit formed in a “<” shape that opens in the direction of the X-axis at the upstream edge (hereinafter sometimes simply referred to as “upstream”) along the scanning direction of the stage 14. 10 are formed at equal intervals. Each slit 28 includes a slit 28 a located on the upstream side and a slit 28 b located on the downstream side. The slit 28a and the slit 28b are orthogonal to each other, and the slit 28a has an angle of −45 degrees and the slit 28b has an angle of +45 degrees with respect to the X axis.

  The position of the slit 28 is substantially coincident with the center of the exposure head 30. Further, the size of each slit 28 is set to sufficiently cover the width of the exposure area 32 by the corresponding exposure head 30. Further, the position of the slit 28 may be substantially coincident with the center position of the overlapping portion between the adjacent exposed regions 34. In this case, the size of each slit 28 is set so as to sufficiently cover the width of the overlapping portion between the exposed regions 34.

  In the position below each slit 28 inside the stage 14, single cell type light detection as a light spot position detecting means for detecting a light spot as a pixel unit in a used pixel part designation process described later. A vessel (not shown) is incorporated. In addition, each photodetector is connected to an arithmetic unit (not shown) as a pixel part selection means for selecting the pixel part in the used pixel part specifying process described later.

  The operation mode of the exposure apparatus at the time of exposure may be a mode in which exposure is continuously performed while the exposure head is constantly moved, or at each movement destination position while the exposure head is moved stepwise. The exposure head may be stationary and the exposure operation may be performed.

<< Exposure head >>
Each exposure head 30 is connected to the scanner 24 so that each pixel portion (micromirror) row direction of an internal digital micromirror device (DMD) 36 described later forms a predetermined set inclination angle θ with the scanning direction. It is attached. For this reason, the exposure area 32 by each exposure head 30 is a rectangular area inclined with respect to the scanning direction. As the stage 14 moves, a strip-shaped exposed region 34 is formed in the photosensitive layer 12 for each exposure head 30. In the example shown in FIGS. 2 and 3B, the scanner 24 includes ten exposure heads arranged in a substantially matrix of 2 rows and 5 columns.
In the following description, when the individual exposure heads arranged in the mth row and the nth column are indicated, the exposure head 30 _mn is indicated, and exposure by the individual exposure heads arranged in the mth row and the nth column is performed. When an area is indicated, it is expressed as an exposure area 32 _mn .

Further, as shown in FIGS. 3A and 3B, each of the exposure heads 30 in each row arranged in a line so that each of the strip-shaped exposed regions 34 partially overlaps the adjacent exposed region 34 is In the arrangement direction, they are shifted by a predetermined interval (a natural number times the long side of the exposure area, twice in this embodiment). Therefore, can not be exposed portion between the exposure area _{32 11} in the first row and the exposure area _{32 12,} it can be exposed by the second row of the exposure area _{32 21.}

  As shown in FIGS. 4 and 5, each of the exposure heads 30 includes a light modulation unit (spatial light modulation element that modulates each pixel unit) that modulates incident light for each pixel unit according to image data. DMD36 (manufactured by Texas Instruments, USA). The DMD 36 is connected to a controller serving as a pixel part control unit including a data processing unit and a mirror drive control unit. The data processing unit of this controller generates a control signal for driving and controlling each micromirror in the use area on the DMD 36 for each exposure head 30 based on the input image data. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 36 for each exposure head 30 based on the control signal generated by the image data processing unit.

  As shown in FIG. 4, on the light incident side of the DMD 36, there is provided a laser emission portion in which the emission end portion (light emission point) of the optical fiber is arranged in a line along the direction that coincides with the long side direction of the exposure area 32. The fiber array light source 38, the lens system 40 for correcting the laser light emitted from the fiber array light source 38 and condensing it on the DMD, and the mirror 42 for reflecting the laser light transmitted through the lens system 40 toward the DMD 36 Arranged in order. In FIG. 4, the lens system 40 is schematically shown.

  As shown in detail in FIG. 5, the lens system 40 has a pair of combination lenses 44 that collimate the laser light emitted from the fiber array light source 38, and the light quantity distribution of the collimated laser light becomes uniform. A pair of combination lenses 46 to be corrected in this way, and a condensing lens 48 that condenses the laser light whose light quantity distribution has been corrected on the DMD 36.

  Further, on the light reflection side of the DMD 36, a lens system 50 that images the laser light reflected by the DMD 36 on the exposed surface of the photosensitive layer 12 is disposed. The lens system 50 includes two lenses 52 and 54 arranged so that the DMD 36 and the exposed surface of the photosensitive layer 12 have a conjugate relationship.

  In the present embodiment, the laser light emitted from the fiber array light source 38 is substantially magnified five times, and then the light from each micromirror on the DMD 36 is reduced to about 5 μm by the lens system 50. Is set to

-Light modulation means-
The light modulation means includes n (where n is a natural number of 2 or more) two-dimensionally arranged picture element portions, and the light modulation means corresponds to the pattern information (also referred to as “pixel data”). There is no particular limitation as long as the pixel part can be controlled, and it can be appropriately selected according to the purpose. For example, a spatial light modulator is preferable.

  Examples of the spatial light modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), and modulates transmitted light by an electro-optic effect. An optical element (PLZT element), a liquid crystal optical shutter (FLC), etc. are mentioned, Among these, DMD is mentioned suitably.

The light modulation means preferably has pattern signal generation means for generating a control signal based on pattern information (pixel data) to be formed. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
As shown in FIG. 6, the DMD 36 is a mirror device in which a large number of micromirrors 58 are arranged in a lattice pattern on a SRAM cell (memory cell) 56 as a pixel portion constituting each pixel (pixel). . In this embodiment, a DMD 36 in which 1024 columns × 768 rows of micromirrors 58 are arranged is used. Among these, the micromirrors 58 that can be driven by a controller connected to the DMD 36, that is, usable micromirrors 58 are 1024 columns × 256 rows. Suppose only. The data processing speed of the DMD 36 is limited, and the modulation speed per line is determined in proportion to the number of micromirrors to be used. Thus, by using only some of the micromirrors in this way, Modulation speed increases. Each micromirror 58 is supported by a support column, and a material having high reflectivity such as aluminum is deposited on the surface thereof. In the present embodiment, the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch thereof is 13.7 μm in both the vertical direction and the horizontal direction. The SRAM cell 56 is of a silicon gate CMOS manufactured in a normal semiconductor memory manufacturing line via a support including a hinge and a yoke, and the whole is configured monolithically (integrated).

  When an image signal representing the density of each point constituting a desired two-dimensional pattern in binary is written in the SRAM cell (memory cell) 56 of the DMD 36, each micromirror 58 supported by the column is centered on the diagonal line. As shown in FIG. 1, the inclination is inclined to ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 36 is disposed. FIG. 7A shows a state in which the micromirror 58 is tilted to + α degrees in the on state, and FIG. 7B shows a state in which the micromirror 58 is tilted to −α degrees in the off state. In this way, by controlling the inclination of the micromirror 58 in each pixel of the DMD 36 as shown in FIG. 6 in accordance with the image signal, the laser light B incident on the DMD 36 moves in the inclination direction of each micromirror 58. Reflected.

  FIG. 6 shows an example in which a part of the DMD 36 is enlarged and each micromirror 58 is controlled to + α degrees or α degrees. The on / off control of each micromirror 58 is performed by the controller connected to the DMD 36. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 58 travels.

-Light irradiation means-
The light irradiation means is not particularly limited and may be appropriately selected depending on the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, fluorescent tube, LED, etc. , A known light source such as a semiconductor laser, or a means capable of combining and irradiating two or more lights. Among these, a means capable of combining and irradiating two or more lights is preferable.
The light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support. In particular, ultraviolet to visible light, electron beam, X-ray, laser beam, and the like can be mentioned. Of these, laser beam is preferable, and a laser combining two or more lights (hereinafter, referred to as “combined laser”). More preferred. Even when light irradiation is performed after the support is peeled off, the same light can be used.

As a wavelength of the ultraviolet to visible light, for example, 300 to 1500 nm is preferable, 320 to 800 nm is more preferable, and 330 nm to 650 nm is particularly preferable.
As a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330 nm-500 nm is still more preferable, 400 nm-450 nm is especially preferable.

  Examples of means capable of irradiating the combined laser include, for example, a plurality of lasers, a multimode optical fiber, and collective optics for condensing the laser beams respectively emitted from the plurality of lasers and coupling them to the multimode optical fiber. Means having a system are preferred.

Hereinafter, means (fiber array light source) capable of irradiating the combined laser will be described with reference to the drawings.
As shown in FIG. 8, the fiber array light source 38 includes a plurality of (for example, 14) laser modules 60, and one end of a multimode optical fiber 62 is coupled to each laser module 60. An optical fiber 64 having a cladding diameter smaller than that of the multimode optical fiber 62 is coupled to the other end of the multimode optical fiber 62. As shown in detail in FIG. 9, seven ends of the optical fiber 64 opposite to the multimode optical fiber 62 are arranged along the direction orthogonal to the scanning direction, and these are arranged in two rows to form the laser emitting unit 66. Is configured.

  As shown in FIG. 9, the laser emitting portion 66 constituted by the end portion of the optical fiber 64 is sandwiched and fixed between two support plates 68 having a flat surface. Moreover, it is desirable that a transparent protective plate such as glass is disposed on the light emitting end face of the optical fiber 64 for protection. The light exit end face of the optical fiber 64 has a high light density and is likely to collect dust and easily deteriorate. However, by arranging the protective plate as described above, it is possible to prevent the dust from adhering to the end face and to delay the deterioration. Can do.

  For example, as shown in FIG. 25, such an optical fiber is formed by coaxially connecting an optical fiber 64 having a length of 1 to 30 cm with a small cladding diameter at the tip portion on the laser light emission side of a multimode optical fiber 62 having a large cladding diameter. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 64 is fused and joined to the outgoing end face of the multimode optical fiber 62 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 64 a of the optical fiber 64 is the same as the diameter of the core 62 a of the multimode optical fiber 62.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused with an optical fiber having a small cladding diameter may be coupled to the output end of the multimode optical fiber 62 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 64 may be referred to as an emission end portion of the multimode optical fiber 62.

  The multimode optical fiber 62 and the optical fiber 64 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. In the present embodiment, the multimode optical fiber 62 and the optical fiber 64 are step index type optical fibers, and the multimode optical fiber 62 has a cladding diameter = 125 μm, a core diameter = 50 μm, NA = 0.2, an incident end face. The transmittance of the coat is 99.5% or more, and the optical fiber 64 has a clad diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2.

  In general, in the laser light in the infrared region, the propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to an infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  However, the cladding diameter of the optical fiber is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber array light source is 125 μm. However, the smaller the clad diameter, the deeper the focal depth, so the clad diameter of the optical fiber is preferably 80 μm or less, more preferably 60 μm or less. 40 μm or less is more preferable. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 64 is preferably 10 μm or more.

  The laser module 60 is composed of a combined laser light source (fiber array light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6 arranged on the heat block 110, And LD7, collimator lenses L1, L2, L3, L4, L5, L6, and L7 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 200, and one multimode. And an optical fiber 62. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

  The GaN-based semiconductor lasers LD1 to LD7 all have the same oscillation wavelength (for example, 405 nm), and the maximum output is also all the same (for example, 100 mW for the multimode laser and 30 mW for the single mode laser). As the GaN-based semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above 405 nm in a wavelength range of 350 nm to 450 nm may be used.

  As shown in FIGS. 27 and 28, the combined laser light source is housed in a box-shaped package 400 having an upper opening together with other optical elements. The package 400 includes a package lid 410 created so as to close the opening. After the degassing process, a sealing gas is introduced, and the package 400 and the package lid are closed by closing the opening of the package 400 with the package lid 410. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by the reference numeral 410.

  A base plate 420 is fixed to the bottom surface of the package 400, and the heat block 110, a condensing lens holder 450 that holds the condensing lens 200, and the multimode optical fiber 62 are disposed on the top surface of the base plate 420. A fiber holder 460 that holds the incident end is attached. The exit end of the multimode optical fiber 62 is drawn out of the package from an opening formed in the wall surface of the package 400.

  A collimator lens holder 440 is attached to the side surface of the heat block 110, and the collimator lenses L1 to L7 are held. An opening is formed in the lateral wall surface of the package 400, and a wiring 470 for supplying a driving current to the GaN semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 28, in order to avoid complication of the drawing, only the GaN semiconductor laser LD7 is numbered among the plurality of GaN semiconductor lasers, and only the collimator lens L7 is numbered among the plurality of collimator lenses. is doing.

  FIG. 29 shows a front shape of a mounting portion of the collimator lenses L1 to L7. Each of the collimator lenses L <b> 1 to L <b> 7 is formed in a shape in which a region including the optical axis of a circular lens having an aspherical surface is cut out in a parallel plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses L1 to L7 are closely arranged in the light emitting point arrangement direction so that the length direction is orthogonal to the light emitting point arrangement direction of the GaN-based semiconductor lasers LD1 to LD7 (left-right direction in FIG. 29).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having a light emission width of 2 μm, and each of the laser beams B1 in a state parallel to the active layer and a divergence angle in a direction perpendicular to the active layer, respectively, for example A laser emitting ~ B7 is used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

Therefore, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses L1 to L7 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses L1 to L7 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. Each of the collimator lenses L1 to L7 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 200 is obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into an elongated shape in a parallel plane, and being long in the arrangement direction of the collimator lenses L1 to L7, that is, in the horizontal direction and short in the direction perpendicular thereto. Is formed. The condensing lens 200 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 200 is also formed by molding resin or optical glass, for example.

  In addition, since the light emitting means for illuminating the DMD uses a high-intensity fiber array light source in which the output ends of the optical fibers of the combined laser light source are arranged in an array, it has a high output and a deep depth of focus. An exposure apparatus can be realized. Furthermore, since the output of each fiber array light source is increased, the number of fiber array light sources required to obtain a desired output is reduced, and the cost of the exposure apparatus can be reduced.

  Further, since the cladding diameter of the output end of the optical fiber is smaller than the cladding diameter of the incident end, the diameter of the light emitting portion is further reduced, and the brightness of the fiber array light source can be increased. Thereby, an exposure apparatus having a deeper depth of focus can be realized. For example, even in the case of ultra-high resolution exposure with a beam diameter of 1 μm or less and a resolution of 0.1 μm or less, a deep depth of focus can be obtained, and high-speed and high-definition exposure is possible. Therefore, it is suitable for a thin film transistor (TFT) exposure process that requires high resolution.

  The light irradiating means is not limited to a fiber array light source including a plurality of the combined laser light sources, and for example, emits laser light incident from a single semiconductor laser having one light emitting point. A fiber array light source in which fiber light sources including optical fibers are arrayed can be used.

  Moreover, as a light irradiation means provided with a plurality of light emitting points, for example, as shown in FIG. An array can be used. Further, a chip-shaped multi-cavity laser 110 shown in FIG. 31A in which a plurality of (for example, five) light emitting points 111a are arranged in a predetermined direction is known. Since the multicavity laser 111 can arrange the light emitting points with high positional accuracy as compared with the case where the chip-shaped semiconductor lasers are arranged, it is easy to multiplex the laser beams emitted from the respective light emitting points. However, as the number of light emitting points increases, the multi-cavity laser 111 is likely to be bent at the time of laser manufacture. Therefore, the number of light emitting points 111a is preferably 5 or less.

  As the light irradiation means, as shown in FIG. 31B, a plurality of multi-cavity lasers 111 are arranged on the heat block 110 in the same direction as the arrangement direction of the light emitting points 111a of each chip. A multi-cavity laser array can be used as a laser light source.

  The combined laser light source is not limited to one that combines laser beams emitted from a plurality of chip-shaped semiconductor lasers. For example, as shown in FIG. 32, a combined laser light source including a chip-shaped multicavity laser 111 having a plurality of (for example, three) emission points 111a can be used. The combined laser light source includes a multi-cavity laser 111, a single multi-mode optical fiber 62, and a condenser lens 200. The multicavity laser 111 can be composed of, for example, a GaN laser diode having an oscillation wavelength of 405 nm.

  In the above-described configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111 a of the multicavity laser 111 is collected by the condenser lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  A plurality of light emitting points 111 a of the multicavity laser 111 are arranged in parallel within a width substantially equal to the core diameter of the multimode optical fiber 62, and a focal point substantially equal to the core diameter of the multimode optical fiber 62 is formed as the condenser lens 200. By using a convex lens of a distance or a rod lens that collimates the outgoing beam from the multicavity laser 111 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multimode optical fiber 62 can be increased. it can.

  As shown in FIG. 33, a multi-cavity laser 111 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 111 are equidistant from each other on the heat block 110. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 111 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 111a of each chip.

  This combined laser light source includes a laser array 140, a plurality of lens arrays 114 arranged corresponding to each multi-cavity laser 111, and a single rod arranged between the laser array 140 and the plurality of lens arrays 114. The lens 113, one multimode optical fiber 130, and a condenser lens 120 are provided. The lens array 114 includes a plurality of microlenses corresponding to the emission points of the multicavity laser 110.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111 a of the plurality of multi-cavity lasers 111 is condensed in a predetermined direction by the rod lens 113 and then each microlens of the lens array 114. It becomes parallel light. The collimated laser beam L is condensed by the condensing lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  Still another example of the combined laser light source will be described. As shown in FIGS. 34A and 34B, this combined laser light source has a heat block 182 having an L-shaped cross section in the optical axis direction mounted on a substantially rectangular heat block 180 and is housed between two heat blocks. A space is formed. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 111 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 111a of each chip. It is arranged and fixed at equal intervals in the same direction as the arrangement direction.

  A concave portion is formed in the substantially rectangular heat block 180, and a plurality of (for example, two) light emitting points (for example, five) are arranged in an array on the upper surface of the space side of the heat block 180. The multi-cavity laser 110 is arranged such that its emission point is located on the same vertical plane as the emission point of the laser chip arranged on the upper surface of the heat block 182.

  On the laser beam emission side of the multi-cavity laser 111, a collimator lens array 184 in which collimator lenses are arranged corresponding to the light emission points 111a of the respective chips is arranged. In the collimating lens array 184, the length direction of each collimating lens coincides with the direction in which the divergence angle of the laser beam is large (the fast axis direction), and the width direction of each collimating lens is the direction in which the divergence angle is small (slow axis direction). They are arranged to match. Thus, by collimating and integrating the collimating lenses, the space utilization efficiency of the laser light can be improved, the output of the combined laser light source can be increased, and the number of parts can be reduced and the cost can be reduced. .

  Further, on the laser beam emitting side of the collimating lens array 184, there is one multimode optical fiber 62 and a condensing lens 200 that condenses and couples the laser beam to the incident end of the multimode optical fiber 62. Has been placed.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111a of the plurality of multi-cavity lasers 111 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and collected. The light is collected by the optical lens 200 and is incident on the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  As described above, the combined laser light source can achieve particularly high output by the multistage arrangement of multicavity lasers and the array of collimating lenses. By using this combined laser light source, a higher-intensity fiber array light source or bundle fiber light source can be formed, which is particularly suitable as a fiber light source constituting the laser light source of the exposure apparatus of the present invention.

  A laser module in which each of the combined laser light sources is housed in a casing and the emission end portion of the multimode optical fiber 62 is pulled out from the casing can be configured.

  In addition, the other end of the multimode optical fiber of the combined laser light source is coupled with another optical fiber having the same core diameter as the multimode optical fiber and a cladding diameter smaller than the multimode optical fiber. However, for example, a multimode optical fiber having a cladding diameter of 125 μm, 80 μm, 60 μm or the like may be used without coupling another optical fiber to the emission end.

<< Used pixel part designation means >>
The used pixel part specifying means includes a light spot position detecting means for detecting the position of a light spot on a surface to be exposed as a pixel unit, and N double exposure based on a detection result by the light spot position detecting means. It is preferable to include at least a pixel part selection unit that selects a pixel part to be used for the realization.
Hereinafter, an example of a method for designating a pixel part used for N-exposure by the used pixel part specifying unit will be described.

(1) Method for designating used picture element part in single exposure head In the present embodiment (1), the exposure apparatus 10 performs double exposure on the photosensitive material 12, and each exposure head 30 A description will be given of a method for designating a used pixel portion for reducing the variation in resolution and density unevenness caused by the mounting angle error and realizing ideal double exposure.

The set inclination angle θ in the column direction of the image element (micromirror 58) with respect to the scanning direction of the exposure head 30 can be used as long as there is no mounting angle error of the exposure head 30 or the like. It is assumed that an angle slightly larger than the angle θ _ideal that is exactly double exposure using 256 lines of pixel parts is adopted.
This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
It becomes. In the present embodiment (1), since s = 256 and N = 2 as described above, the angle θ _ideal is about 0.45 degrees according to Equation 3. Therefore, for example, an angle of about 0.50 degrees may be employed as the set inclination angle θ. It is assumed that the exposure apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

  FIG. 10 is an explanatory diagram showing an example of unevenness in the pattern on the exposed surface due to the influence of the mounting angle error of one exposure head 30 and pattern distortion in the exposure apparatus 10 initially adjusted as described above. It is. In the following drawings and description, the light spot in the m-th row is represented by r (m) with respect to the light spot generated by each pixel part (micromirror) and constituting the exposure area on the exposed surface. ), The light spot in the nth column is denoted as c (n), and the light spot in the mth row and the nth column is denoted as P (m, n).

The upper part of FIG. 10 shows a pattern of light spot groups from the usable micromirrors 58 projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary, and the lower part is the upper part. 2 shows the state of the exposure pattern formed on the surface to be exposed when the stage 14 is moved and continuous exposure is performed in the state where the pattern of light spots as shown in FIG.
In FIG. 10, for convenience of explanation, the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns of the micromirrors 58 that can be used are shown separately. Two exposure patterns are superimposed.

In the example of FIG. 10, as a result of adopting the set inclination angle θ slightly larger than the angle θ _ideal , and because it is difficult to finely adjust the mounting angle of the exposure head 30, the actual mounting angle and the above As a result of the error in the set inclination angle θ, density unevenness occurs in any region on the exposed surface. Specifically, in the overlapped exposure region on the exposed surface, which is formed by a plurality of pixel part rows in both the exposure pattern by the odd-numbered micromirrors and the exposure pattern by the even-numbered micromirrors, it is ideal. Overexposure occurs with respect to double exposure, resulting in a redundant drawing area and uneven density.

Further, the example of FIG. 10 is an example of pattern distortion appearing on the exposed surface, and “angular distortion” is generated in which the inclination angle of each pixel row projected on the exposed surface is not uniform. Causes of such angular distortion include various aberrations and alignment deviations of the optical system between the DMD 36 and the exposed surface, distortion of the DMD 36 itself, micromirror placement errors, and the like.
The angular distortion appearing in the example of FIG. 10 is a distortion in which the tilt angle with respect to the scanning direction is smaller in the left column of the figure and larger in the right column of the figure. As a result of this angular distortion, the overexposed area is smaller on the exposed surface shown on the left side of the figure and larger on the exposed surface shown on the right side of the figure.

In order to reduce the density unevenness in the overlapped exposure area on the exposed surface formed by a plurality of pixel part rows as described above, a set of the slit 28 and the photodetector is used as the light spot position detecting means. The actual inclination angle θ ′ is specified for each exposure head 30, and based on the actual inclination angle θ ′, the calculation device connected to the photodetector as the pixel portion selection unit is used for actual exposure. A process of selecting a micromirror to be used is performed.
The actual tilt angle θ ′ is based on at least two light spot positions detected by the light spot position detecting means, and the column direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted. It is specified by the angle formed by.
Hereinafter, the specification of the actual inclination angle θ ′ and the used pixel selection process will be described with reference to FIGS.

-Specification of actual inclination angle θ'-
FIG. 11 is a top view showing the positional relationship between the exposure area 32 by one DMD 36 and the corresponding slit 28. The size of the slit 28 is set to sufficiently cover the width of the exposure area 32.
In the example of the present embodiment (1), the angle formed by the 512th light spot row positioned substantially at the center of the exposure area 32 and the scanning direction of the exposure head 30 is measured as the actual inclination angle θ ′. . Specifically, the micromirrors 58 in the first row and the 512th column on the DMD 36 and the micromirrors 58 in the 256th row and the 512th column are turned on, and the light spots on the exposure surface corresponding to each of the micromirrors 58 are turned on. The positions of P (1,512) and P (256,512) are detected, and the angle formed by the straight line connecting them and the scanning direction of the exposure head is specified as the actual inclination angle θ ′.

FIG. 12 is a top view illustrating a method for detecting the position of the light spot P (256, 512).
First, in a state where the micromirror 58 in the 256th row and the 512th column is turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 512) is changed. The slit 28 is positioned at an arbitrary position so as to be between the upstream slit 28a and the downstream slit 28b. At this time, the coordinates of the intersection of the slit 28a and the slit 28b are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. 12 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 12, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 12 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 12, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 512) on the surface to be exposed are X = X0 + (Y1-Y2) / 2, Y = (Y1 + Y2) / 2. Determine by calculation. By the same measurement, coordinates indicating the position of P (1,512) are also determined, an inclination angle formed by a straight line connecting the respective coordinates and the scanning direction of the exposure head 30 is derived, and this is obtained as an actual inclination angle θ ′. As specified.

-Selection of used pixel part-
The arithmetic unit connected to the photodetector using the actual inclination angle θ ′ specified in this way is
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived, and the first to T-th row micromirrors on the DMD 36 are selected as micromirrors that are actually used during the main exposure. As a result, in the exposure region near the 512th column, a micromirror that minimizes the total area of the overexposed region and the underexposed region with respect to the ideal double exposure is actually obtained. It can be selected as a micromirror to be used for.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number equal to or greater than the value t may be derived. In that case, in the exposure region near the 512th column, a micromirror that minimizes the area of the overexposed region and does not produce an underexposed region with respect to ideal double exposure. It can be selected as a micromirror to be actually used.
It is also possible to derive the maximum natural number equal to or less than the value t. In that case, in the exposure region near the 512th row, a micromirror that minimizes the area of the underexposed region and does not produce an overexposed region with respect to ideal double exposure, It can be selected as a micromirror to be actually used.

FIG. 13 shows how the unevenness on the exposed surface shown in FIG. 10 is improved in the exposure performed using only the light spot generated by the micromirror selected as the micromirror to be actually used as described above. It is explanatory drawing which showed what was done.
In this example, it is assumed that T = 253 is derived as the natural number T and the micromirrors in the first row to the 253rd row are selected. For the micromirrors in the 254th to 256th lines that are not selected, the pixel part control means sends a signal for setting the angle to the always-off state. Not involved in exposure. As shown in FIG. 13, in the exposure region near the 512th column, overexposure and underexposure are almost completely eliminated, and uniform exposure very close to ideal double exposure is realized.

On the other hand, in the left region of FIG. 13 (near c (1) in the figure), the inclination angle of the light spot sequence on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. This is smaller than the inclination angle of the light beam row in the region. Therefore, in the exposure using only the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, an ideal double is applied to each of the exposure pattern of the even-numbered column and the exposure pattern of the odd-numbered column. An area that is underexposed with respect to the exposure is slightly generated.
However, in the actual exposure pattern in which the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in FIG. The effect of offsetting can be minimized.

Further, in the region on the right side of FIG. 13 (near c (1024) in the figure), the inclination angle of the light beam on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. It is larger than the inclination angle of the light beam row in the region. Therefore, in the exposure with the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, as shown in the figure, there is an overexposed region with respect to the ideal double exposure. It will occur slightly.
However, in the actual exposure pattern formed by overlaying the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the regions that are overexposed are complemented with each other, and the density unevenness due to the angular distortion is caused by the double exposure. The effect of offsetting can be minimized.

In the present embodiment (1), as described above, the actual inclination angle θ ′ of the 512th ray array is measured, and based on the T derived from the equation (4) using the actual inclination angle θ ′. The micro-mirror 58 to be used is selected. However, as a method of specifying the actual inclination angle θ ′, a plurality of actual directions formed by the column direction (light spot column) of the plurality of image elements and the scanning direction of the exposure head are used. Each of the tilt angles is measured, and any one of the average value, median value, maximum value, and minimum value is specified as an actual tilt angle θ ′. It is good also as a form to select.
When the average value or the median value is set to the actual inclination angle θ ′, it is possible to realize exposure with a good balance between an overexposed area and an underexposed area with respect to an ideal N-fold exposure. For example, the total area of the overexposed region and the underexposed region is minimized, and the number of pixel units (number of light spots) in the overexposed region and the underexposed region are drawn. It is possible to realize exposure such that the number of prime units (number of light spots) is equal.
Further, if the maximum value is set to the actual inclination angle θ ′, it is possible to realize an exposure that places more importance on eliminating an overexposed region with respect to an ideal N double exposure, for example, an underexposure. It is possible to realize exposure that minimizes the area of the region and does not generate an overexposed region.
Further, if the minimum value is set to the actual inclination angle θ ′, it is possible to realize exposure that places more importance on eliminating underexposed areas with respect to ideal N-fold exposure, for example, overexposure. It is possible to realize exposure that minimizes the area of the region and does not cause a region that is underexposed.

On the other hand, the specification of the actual inclination angle θ ′ is not limited to the method based on the positions of at least two light spots in the same pixel part row (light spot row). For example, the angle obtained from the position of one or more light spots in the same pixel part sequence c (n) and the position of one or more light spots in a row near the c (n), The actual inclination angle θ ′ may be specified.
Specifically, one light spot position in c (n) and one or a plurality of light spot positions included in a light spot row on a straight line and in the vicinity along the scanning direction of the exposure head are detected. The actual inclination angle θ ′ can be obtained from the position information. Further, the angle obtained based on the position of at least two light spots (for example, two light spots arranged so as to straddle c (n)) in the light spot array in the vicinity of the c (n) array is an actual inclination. You may specify as angle (theta) '.

  As described above, according to the specification method of the used pixel portion of the present embodiment (1) using the exposure apparatus 10, resolution variation and density unevenness due to the influence of the mounting angle error of each exposure head and pattern distortion are reduced. In addition, an ideal N-fold exposure can be realized.

(2) Method for designating used pixel parts between a plurality of exposure heads <1>
In the present embodiment (2), the exposure apparatus 10 performs double exposure on the photosensitive material 12, and is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads 30. In the connection region, the variation in resolution and density unevenness due to the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state are reduced, and the ideal A description will be given of a method for designating a used pixel portion for realizing a typical double exposure.

As the set inclination angle θ of each exposure head 30, that is, each DMD 36, the usable pixel portion micromirror 58 of 1024 columns × 256 rows is used if there is no ideal mounting angle error of the exposure head 30. Then, it is assumed that an angle θ _ideal that is exactly double exposure is adopted.
This angle θ _ideal is obtained from the above equations 1 to 3 in the same manner as in the above embodiment (1). In the present embodiment (2), it is assumed that the exposure apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 becomes this angle θ _ideal .

FIG. 14 shows the influence of the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state in the exposure apparatus 10 initially adjusted as described above. FIG. 6 is an explanatory diagram showing an example of density unevenness generated in a pattern on the exposed surface. The displacement of the relative position of each exposure head in the X-axis direction can occur because it is difficult to finely adjust the relative position between the exposure heads.

14 is projected onto the exposed surface of the photosensitive material 12 in a state where the stage 14 is stationary, the light spot group from the usable micromirror 58 of the DMD 36 of the exposure heads 30 ₁₂ and 30 _21. It is the figure which showed these patterns. The lower part of FIG. 14 shows the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing. The state is shown for exposure areas 32 ₁₂ and 32 ₂₁ .
In FIG. 14, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

In the example of FIG. 14, the exposure pattern by the pixel column group A and the pixel column group B as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ in the X-axis direction from the ideal state. In both of the above exposure patterns, a portion where the exposure amount is larger than the ideal double exposure state occurs in the connection area between the heads in the exposure areas 32 ₁₂ and 32 ₂₁ .

In order to reduce density unevenness appearing in the inter-head connecting region formed on the exposed surface by the plurality of exposure heads as described above, in this embodiment (2), a slit is used as the light spot position detecting means. 28 and a set of photodetectors, the positions of some of the light spots constituting the connecting area between the heads formed on the exposed surface among the light spot groups from the exposure heads 30 ₁₂ and 30 _21. Detect (coordinates). Based on the position (coordinates), processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to the photodetector as the pixel portion selection means.

-Detection of position (coordinates)-
FIG. 15 is a top view showing the positional relationship between the exposure areas 32 ₁₂ and 32 ₂₁ similar to those in FIG. 14 and the corresponding slits 28. The size of the slit 28 is large enough to cover the width of the overlapping portion between the exposed areas 34 by the exposure heads 30 ₁₂ and 30 ₂₁ , that is, the slit 28 is formed on the exposed surface by the exposure heads 30 ₁₂ and 30 _21. The size is sufficient to cover the connection area between the heads.

Figure 16 is a top view for explaining a detection method of detecting the position of a point P of the exposure area _{32 21} as an example (256, 1024).
First, with the micromirror in the 256th row and the 1024th column turned on, the stage 14 is slowly moved to move the slit 28 relatively along the Y-axis direction, and the light spot P (256, 1024) is upstream. The slit 28 is positioned at an arbitrary position so as to be between the slit 28a on the side and the slit 28b on the downstream side. At this time, the coordinates of the intersection of the slit 28a and the slit 28b are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. 16 along the Y axis. Then, as indicated by the two-dot chain line in FIG. 16, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 1024).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 16 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 16, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the light spot P (256, 1024).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 1024) on the exposed surface are calculated as X = X0 + (Y1−Y2) / 2, Y = (Y1 + Y2) / 2. Determined by

-Identification of unused pixel parts-
In the example of FIG. 14, first, the position of the point P of the exposure area _{32 12} (256,1) is detected by a set of slits 28 and a photodetector as the light spot position detecting unit. Subsequently, the position of each light spot on the 256 line of light spots row r of the exposure area _{32 21 (256), P (} 256,1024), to detect the P (256,1023) ··· and order periodically, where the exposure area _{32 21} of point P indicating the exposure area _{32 12} point P (256,1) larger X coordinate than the (256, n) is detected, and terminates the detecting operation. Then, to identify the micro mirrors corresponding to light spots constituting the c (1024) from the point light spot column c of the exposure area 32 ₂₁ (n + 1), as a micro-mirror is not used during the exposure (unused pixel parts) .
For example, in FIG. 14, the exposure area _{32 21} point P (256,1020) is shows a larger X coordinate than the point P of the exposure area _{32 12} (256,1) of the exposure area _{32 21} spot If P (256,1020) is that the detection operation at the detected ended, the light spots constituting the first 1024 lines from the 1021 line of exposure area _{32 21,} corresponding to the portion 70 covered with hatched in FIG. 17 The corresponding micromirror is identified as a micromirror that is not used during the main exposure.

Next, the number N of the N multiple exposure, the position of the point P of the exposure area _{32 12} (256, N) is detected. In this embodiment (2), since N = 2, the position of the light spot P (256, 2) is detected.
Then, among the light spot columns of the exposure area 32 _21, except those identified as light spots string corresponding to the micromirrors is not used during the exposure in the above, the position of the light spot constituting the rightmost 1020 column a, P (1,1020) in order from P (1,1020), P (2,1020 ) ··· and continue to detection, greater than the point P of the exposure area _{32 12} (256,2) X When the light spot P (m, 1020) indicating the coordinates is detected, the detection operation is terminated.
Thereafter, the connected operational devices to said light detector, and X-coordinate of the exposure area _{32 12} of the light spot P (256, two), point P of the exposure area _{32 21} (m, 1020) and P (m- and X-coordinate of 1,1020) are compared, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m, 1020) is closer to the X coordinate of the point P in the exposure area _{32 12} (256, 2) a micro mirror corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020) is identified as a micro-mirror is not used during the exposure.
Also, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m-1,1020) is close to the X-coordinate of the point P in the exposure area _{32 12} (256, 2), the light of the exposure area _{32 21} Micromirrors corresponding to points P (1, 1020) to P (m−2, 1020) are specified as micromirrors that are not used for the main exposure.
Furthermore, the position of the point P of the exposure area _{32 12 (256, N-1} ) That point P (256,1), the position of each point constituting the first 1019 column is the next row of the exposure area _{32 21} The same detection process and identification of micromirrors that are not used are also performed.

  As a result, for example, micromirrors corresponding to the light spots that form the shaded area 72 in FIG. 17 are added as micromirrors that are not used during actual exposure. These micromirrors are always signaled to set the micromirror angle to the off-state angle, and these micromirrors are substantially not used for exposure.

As described above, the micromirrors that are not used at the time of actual exposure are identified, and the micromirrors that are not used at the time of actual exposure are selected as the micromirrors that are used at the time of actual exposure, whereby the exposure areas 32 ₁₂ and 32 ₂₁ In the connecting area between the heads, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure can be minimized. As shown in the lower part of FIG. Uniform exposure extremely close to double exposure can be realized.

In the above example, upon the particular light spots constituting the regions 72 covered with hatched in FIG. 17, the X coordinate of the point P in the exposure area _{32 12} (256, 2), the exposure area _{32 21} of the light spot P (m, 1020) and P (m-1,1020) without comparison of the X-coordinate of the immediately, P from point P of the exposure area _{32 21 (1,1020) (m-} 2 , 1020) may be specified as a micromirror that is not used during the main exposure. In that case, in the connecting area between the heads, a micromirror is actually used that minimizes the area of the overexposed area with respect to the ideal double exposure and does not generate an underexposed area. It can be selected as a micromirror.
Further, the micro-mirrors corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020), it may be specified as micro mirrors not used in this exposure. In that case, in the connecting region between the heads, a micromirror is used in which the area of the region that is underexposed with respect to the ideal double exposure is minimized and the region that is not overexposed does not occur. It can be selected as a micromirror.
Further, in the connecting area between the heads, the number of pixel units (the number of light points) in an area that is overexposed with respect to an ideal double drawing and the number of pixel units (the number of light points) in an area that is underexposed. It is good also as selecting the micromirror actually used so that it may become equal.

  As described above, according to the method for designating the used pixel portion of the present embodiment (2) using the exposure apparatus 10, the resolution variation and the density due to the relative position shift in the X-axis direction of the plurality of exposure heads. Unevenness can be reduced and ideal N-fold exposure can be realized.

(3) Specification method of used pixel parts between a plurality of exposure heads <2>
In the present embodiment (3), the exposure apparatus 10 performs double exposure on the photosensitive material 12 and is an overlapped exposure area on the exposed surface formed by a plurality of exposure heads 30. In the joint region, the relative position of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) from the ideal state in the X-axis direction, the mounting angle error of each exposure head, and the distance between the two exposure heads A description will be given of a method for designating a used pixel part for reducing the variation in resolution and density unevenness due to the relative mounting angle error of the lens and realizing ideal double exposure.

As the set tilt angle of each exposure head 30, that is, each DMD 36, in an ideal state where there is no mounting angle error of the exposure head 30, a usable 1024 column × 256 row pixel element (micromirror 58) is provided. It is assumed that an angle slightly larger than the angle θ _ideal that is used for exactly double exposure is adopted.
This angle θ _ideal is a value obtained in the same manner as the above embodiment (1) using the above equations 1 to 3, and in this embodiment, s = 256 and N = 2 as described above. The angle θ _ideal is about 0.45 degrees. Therefore, for example, an angle of about 0.50 degrees may be employed as the set inclination angle θ. It is assumed that the exposure apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

FIG. 18 shows the mounting angle errors of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the exposure apparatus 10 in which the mounting angles of the exposure heads 30, that is, the DMDs 36 are initially adjusted as described above. It is an explanatory view showing an example of unevenness generated in a pattern on an exposed surface due to the influence of the relative mounting angle error between the exposure heads 30 ₁₂ and 30 ₂₁ and the shift of the relative position.

In the example of FIG. 18, as in the example of FIG. 14, as a result of the shift of the relative positions of the exposure heads 30 ₁₂ and 30 _{21 in} the X-axis direction, exposure by every other light spot group (pixel column groups A and B) is performed. In both exposure patterns 32 ₁₂ and 32 ₂₁ , the exposure amount overlaps on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface of the exposure areas 32 ₁₂ and 32 ₂₁ , which is more than the ideal double exposure state. A region 74 is generated, which causes uneven density.
Further, in the example of FIG. 18, it is difficult to finely adjust the result of setting the tilt angle θ of each exposure head slightly larger than the angle θ _ideal satisfying the formula (1) and the mounting angle of each exposure head. Therefore, as a result of the actual mounting angle deviating from the set inclination angle θ, even in regions other than the exposure region overlapping on the coordinate axis orthogonal to the scanning direction of the exposure head on the exposed surface, In the connection region between the pixel part columns, which is an overlapped exposure region on the exposed surface, formed by a plurality of pixel part columns, both in the exposure pattern by every other light spot group (pixel column groups A and B). A region 76 that is overexposed than the ideal double exposure state is generated, and this causes further density unevenness.

In this embodiment (3), first, the use pixel selection process for reducing the uneven density due to the influence of the deviation of the mounting angle error and relative mounting angle of the exposure heads 30 ₁₂ and 30 _21.
Specifically, a set of a slit 28 and a photodetector is used as the light spot position detecting means, and an actual inclination angle θ ′ is specified for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the actual inclination angle θ ′ is set. Based on this, it is assumed that processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to a photodetector as the pixel part selection means.

-Specification of actual inclination angle θ'-
The actual inclination angle θ ′ is specified with respect to the positions of the light spots P (1, 1) and P (256, 1) in the exposure area 32 ₁₂ for the exposure head 30 _{12 and in the} exposure area 32 ₂₁ for the exposure head 30 ₂₁ . The positions of the light spots P (1,1024) and P (256,1024) are detected by the combination of the slit 28 and the photodetector used in the above-described embodiment (2), and the inclination angle of the straight line connecting them. And the angle formed by the scanning direction of the exposure head.

-Identification of unused pixel parts-
The arithmetic device connected to the photodetector using the actual inclination angle θ ′ thus specified is similar to the following equation 4 similar to the arithmetic device in the embodiment (1) described above.
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the micromirrors in the (T + 1) th to 256th rows on the DMD 36 are not used for the main exposure. Processing to identify as a micromirror is performed.
For example, T = 254 for the exposure head _{30 12,} when T = 255 was derived for the exposure head _3O21, micro mirrors corresponding to light spots constituting the parts 78 and 80 covered with hatched in FIG. 19 These are specified as micromirrors that are not used for the main exposure. As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure is minimized. be able to.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number equal to or greater than the value t may be derived. In this case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area where the amount is excessive and to prevent an area where the exposure amount is insufficient.
Or it is good also as deriving the maximum natural number below value t. In this case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area of the insufficient region and prevent the region from being overexposed.
In each area other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads, the number of pixel units (light It is also possible to identify micromirrors that are not used during the main exposure so that the number of pixel units (the number of light points) in the underexposed region is equal to the number of points.

Thereafter, with respect to the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with diagonal lines in FIG. 19, the same processing as that of the present embodiment (3) described with reference to FIGS. In FIG. 19, the micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 are identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors specified as not used at the time of exposure, the pixel element control means sends a signal for setting the angle to the always-off state, and these micromirrors are substantially exposed. Not involved.

  As described above, according to the method for designating the used picture element portion of the present embodiment (3) using the exposure apparatus 10, the relative position shifts in the X-axis direction of the plurality of exposure heads and the mounting angles of the exposure heads Variations in resolution and density unevenness due to errors and relative mounting angle errors between exposure heads can be reduced, and ideal N-fold exposure can be realized.

  Although the above-described drawing element portion specifying method by the exposure apparatus 10 has been described in detail, the above embodiments (1) to (3) are merely examples, and various modifications can be made without departing from the scope of the present invention. is there.

  In the above embodiments (1) to (3), as a means for detecting the position of the light spot on the exposed surface, a set of the slit 28 and the single cell type photodetector is used. The present invention is not limited to this, and any form may be used. For example, a two-dimensional detector may be used.

  Further, in the above embodiments (1) to (3), the actual inclination angle θ ′ is obtained from the position detection result of the light spot on the exposed surface by the combination of the slit 28 and the photodetector, and the actual inclination angle θ ′ is obtained. The micromirrors to be used are selected based on the above, but a usable micromirror may be selected without the derivation of the actual inclination angle θ ′. Furthermore, for example, the reference exposure using all available micromirrors is performed, and the micromirror used by the operator is manually specified by checking the resolution and density unevenness by visual observation of the reference exposure results. It is included in the scope of the invention.

In addition to the angular distortion described in the above example, there are various forms of pattern distortion that can occur on the exposed surface.
As an example, as shown in FIG. 20A, there is a form of magnification distortion in which light rays from each micromirror 58 on the DMD 36 reach the exposure area 32 on the exposure surface at different magnifications.
As another example, as shown in FIG. 20B, there is a form of beam diameter distortion in which the light from each micromirror 58 on the DMD 36 reaches the exposure area 32 on the exposed surface with a different beam diameter. . These magnification distortion and beam diameter distortion are mainly caused by various aberrations and alignment deviation of the optical system between the DMD 36 and the exposed surface.
As yet another example, there is a form of light amount distortion in which light beams from the micromirrors 58 on the DMD 36 reach the exposure area 32 on the exposed surface with different light amounts. In addition to various aberrations and misalignment, this light amount distortion is caused by the positional dependence of the transmittance of the optical element between the DMD 36 and the exposed surface (for example, the lenses 52 and 54 in FIG. 5 which is a single lens) and the light amount by the DMD 36 itself. Caused by unevenness. These forms of pattern distortion also cause unevenness in resolution and density in the pattern formed on the exposed surface.

  According to the above embodiments (1) to (3), the residual elements of pattern distortion in these forms after selecting the micromirrors actually used for the main exposure are the same as the residual elements of angular distortion described above. It is possible to level out by the effect of filling by multiple exposure, and the unevenness of resolution and density can be reduced over the entire exposure area of each exposure head.

<< Reference exposure >>
As a modified example of the above-described embodiments (1) to (3), among the usable micromirrors, (N-1) every micromirror column, or 1 / N rows of all light spot rows. A reference exposure is performed using only a group of micromirrors constituting an adjacent row, and among the micromirrors used for the reference exposure, micromirrors that are not used at the time of actual exposure are specified so that uniform exposure can be realized. It is good as well.
The result of the reference exposure by the reference exposure means is output as a sample, and the output reference exposure result is analyzed to confirm resolution variation and density unevenness and to estimate the actual inclination angle. The analysis of the result of the reference exposure may be a visual analysis by an operator.

FIG. 21 is an explanatory diagram showing an example of a form in which reference exposure is performed using only (N-1) rows of micromirrors using a single exposure head.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the odd-numbered light spot arrays indicated by the solid lines in FIG. 21A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, it is possible to specify a micromirror to be used in the main exposure by confirming variations in resolution and density unevenness, or estimating an actual inclination angle.
For example, micromirrors other than the micromirror corresponding to the light spot array shown by hatching in FIG. 21B are designated as actually used in the main exposure among the micromirrors constituting the odd light spot array. . For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and the micromirror used during the main exposure may be designated, or the same pattern as that for the odd-numbered light spot arrays may be applied. Good.
By specifying the micromirrors used in the main exposure as described above, in the main exposure using both the odd-numbered and even-numbered micromirrors, a state close to ideal double exposure can be realized.

FIG. 22 is an explanatory diagram showing an example of a form in which reference exposure is performed using only a plurality of (N-1) rows of micromirrors using a plurality of exposure heads.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference is made using only the micromirrors corresponding to the odd-numbered light spot rows of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction, which are indicated by solid lines in FIG. Exposure is performed, and a reference exposure result is output as a sample. Based on the output reference exposure result, the variation in resolution and density unevenness in the region other than the head-to-head connection region formed on the exposed surface by the two exposure heads are confirmed, or the actual inclination angle is estimated. Thus, the micromirror to be used at the time of the main exposure can be designated.
For example, the micromirrors other than the micromirrors corresponding to the light spot rows in the area 86 shown by hatching in FIG. 22 and the shaded area 88 are the micromirrors constituting the light spots in the odd rows, during the main exposure. Specified as actually used. For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and a micromirror used in the main exposure may be designated, or the same pattern as that for the odd-numbered pixel columns may be applied. Good.
In this way, in the main exposure using both the odd-numbered and even-numbered micromirrors by designating the micromirrors that are actually used during the main exposure, the two exposure heads form the surface to be exposed. A state close to ideal double exposure can be realized in a region other than the head-to-head connection region.

FIG. 23 is an explanatory diagram showing an example of a form in which reference exposure is performed using a single exposure head and using only micromirror groups constituting adjacent rows corresponding to 1 / N rows of the total light spot rows. It is.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only micromirrors corresponding to the light spots in the first to 128 (= 256/2) rows indicated by the solid line in FIG. 23A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, a micromirror to be used in the main exposure can be designated.
For example, a micromirror other than the micromirror corresponding to the light spot group indicated by hatching in FIG. 23B is designated as actually used in the main exposure among the micromirrors in the first to 128th rows. Can be done. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used in the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
By designating the micromirror to be used at the time of the main exposure in this way, a state close to an ideal double exposure can be realized in the main exposure using the entire micromirror.

FIG. 24 uses a plurality of exposure heads, and two adjacent exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction are adjacent to each other corresponding to 1 / N rows of the total number of light spots. It is explanatory drawing which showed an example of the form which performs reference exposure using only the micromirror group which comprises a line.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the light spots in the first to 128th (= 256/2) rows indicated by solid lines in FIG. 24, and the reference exposure results are output as samples. . Based on the reference exposure result outputted from the sample, it is possible to realize the main exposure in which the variation in resolution and the density unevenness in the area other than the joint area between the heads formed on the exposed surface by the two exposure heads are minimized. In addition, it is possible to designate a micromirror to be used during the main exposure.
For example, micromirrors other than the micromirrors corresponding to the light spot arrays in the region 90 shown by hatching in FIG. 24 and the region 92 shown by shading are included in the micromirrors in the first to 128th rows. Designated as actually used at the time of exposure. For the micromirrors in the 129th to 256th lines, reference exposure may be separately performed in the same manner, and the micromirrors used for the main exposure may be designated, or the micromirrors in the first to 128th lines may be designated. The same pattern as that for the mirror may be applied.
In this way, by specifying the micromirror to be used in the main exposure, a state close to ideal double exposure is realized in the area other than the inter-head connecting area formed on the exposed surface by the two exposure heads. it can.

  In the above embodiments (1) to (3) and the modified examples, the case where the main exposure is the double exposure has been described. However, the present invention is not limited to this, and any multiple exposure more than the double exposure may be used. . In particular, by setting the exposure to about 3 to 7 exposures, high resolution can be secured, and exposure with reduced variations in resolution and density unevenness can be realized.

  Further, in the exposure apparatus according to the embodiment and the modified example, the dimension of the predetermined part of the two-dimensional pattern represented by the image data is matched with the dimension of the corresponding part that can be realized by the selected use pixel. A mechanism for converting image data is preferably provided. By converting the image data in this way, a high-definition pattern according to a desired two-dimensional pattern can be formed on the exposed surface.

[Development process]
The developing step includes a step of developing the photosensitive layer by exposing the photosensitive layer by the exposing step and removing an unexposed portion.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, alkaline aqueous solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

The pH of the weak alkaline aqueous solution is, for example, preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include 0.1 to 5% by mass of sodium carbonate aqueous solution or potassium carbonate aqueous solution, 0.01 to 0.1% by mass of potassium hydroxide aqueous solution, and the like.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

The development method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paddle development, shower development, shower & spin development, and dip development.
Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the exposed photosensitive resin layer by shower. In addition, it is preferable to spray an alkaline liquid having low solubility of the photosensitive resin layer by a shower or the like before development to remove the thermoplastic resin layer, the intermediate layer, or the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the processes in a well-known color filter manufacturing method is mentioned, For example, a hardening process process etc. are mentioned. These may be used alone or in combination of two or more.

-Curing process-
It is preferable to provide a curing treatment step for performing a curing treatment on the photosensitive layer after the development step.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the pattern is formed after the developing step. By the entire surface exposure, curing of the resin in the photosensitive composition forming the photosensitive layer is accelerated, and the surface of the formed pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the pattern is formed after the developing step. The whole surface heating increases the film strength of the surface of the pattern.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

  The color filter manufacturing method of the present invention can form a pattern with high definition and efficiency by suppressing distortion of an image formed on the exposed surface of the photosensitive layer. It can be suitably used for forming various required patterns, and can be particularly suitably used for forming a high-definition color filter pattern.

In the method for producing a color filter of the present invention, as described above, the pixels of the three primary colors RGB can be arranged in a mosaic or stripe pattern on a transparent substrate such as a glass substrate by the pattern forming method of the present invention. it can.
There is no restriction | limiting in particular as a dimension of each pixel, According to the objective, it can select suitably, For example, it is preferable to set it as 40-200 micrometers. In the case of a stripe shape, a width of 40 to 200 μm is usually used.
As a method for producing the color filter, for example, using a photosensitive layer colored black on a transparent substrate, exposure and development were performed to form a black matrix, and then the color filter was colored in one of the three primary colors of RGB. A color in which the three primary colors of RGB are arranged in a mosaic or stripe pattern on the transparent substrate by repeating exposure and development sequentially for each color in a predetermined arrangement with respect to the black matrix using a photosensitive layer. The method of forming a filter is mentioned.

(Color filter)
The color filter of the present invention is manufactured by the method for manufacturing the color filter of the present invention.
The color filter has a pigment C.I. I. Pigment Red 254, green (G) coloring pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 139, as well as blue (B) coloring pigment C.I. I. When manufactured using CI Pigment Blue 15: 6, the chromaticities of all the single colors of red (R), green (G), and blue (B) by the D65 light source are, for example, values shown in Table 1 below. It becomes. Within this range, the colors of the reflection mode and the transmission mode are balanced.

Here, the chromaticity is measured by a microspectroscopy hardness meter (manufactured by Olympus Optical Co., Ltd., OSP100 or 200), calculated as a result of a D65 light source field of view of 2 degrees, and expressed as an xyY value of the xyz color system. Further, the difference from the target chromaticity is represented by the ΔEab value of the La ^* b ^* color system.

  The color filter has a pigment C.I. I. Pigment red 254 and C.I. I. Pigment Red 177, pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 150, and blue (B) coloring pigment C.I. I. Pigment blue 15: 6 and C.I. I. When manufactured using Pigment Violet 23, the chromaticities of all the single colors of red (R), green (G), and blue (B) by the F10 light source are, for example, the values shown in Table 2 below. . If it is this range, it is preferable as a color filter for TV with a wide color reproduction range and high color temperature.

Here, the chromaticity is measured with a microspectroscopy hardness meter (manufactured by Olympus Optical Co., Ltd., OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value of the xyz color system. Further, the difference from the target chromaticity is represented by the ΔEab value of the La ^* b ^* color system.

(Display device)
The display device according to the present invention includes the color filter according to the present invention, in which liquid crystal is sealed between a pair of substrates arranged to face each other, and further includes other members as necessary. Become.
The color filter of the present invention is intended to be formed on the counter substrate of the liquid crystal display device (the substrate on the side where there is no active element such as TFT), and is also a COA method formed on the TFT substrate side, and only black on the TFT substrate side. A BOA method for forming the layer or an HA method having a high aperture structure on the TFT substrate can also be used.

An overcoat film or a transparent conductive film can be further formed on the color filter as necessary. Thereafter, liquid crystal is sealed between the color filter and the counter substrate, and a liquid crystal display device is manufactured.
The liquid crystal display method to be applied is not particularly limited and is appropriately selected depending on the purpose. For example, ECB (Electrically Controlled Birefringence), TN (Twisted Nematic), OCB (Optically Compensatory Bend), VA (Vertically Aligned), HAN (Hybrid Aligned Nematic), STN (Supper Twisted Nematic), IPS (In-Plane Switching), GH (Guest Host), FLC (ferroelectric liquid crystal), AFLC (antiferroelectric liquid crystal), and PDLC (Polymer dispersed liquid crystal).

  The basic configuration of the display device includes (1) a driving side substrate in which driving elements such as thin film transistors (hereinafter referred to as “TFTs”) and pixel electrodes (conductive layers) are arranged, a color filter, A color filter side substrate provided with a counter electrode (conductive layer) is disposed opposite to each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap, and (2) the color filter is directly on the drive side substrate. Examples include a configuration in which the formed color filter integrated drive substrate and a counter substrate including a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap portion. .

The display device of the present invention can display a clear color in both the transmission mode and the reflection mode by using the color filter of the present invention having a good chromaticity in the D65 light source field of view of 2 degrees. And a device such as a portable terminal and a portable game machine that also use the reflection mode.
In addition, the display device of the present invention can achieve high color purity and color temperature by using the color filter of the present invention having good chromaticity in the F10 light source field of view of 2 degrees. It can be suitably used for a liquid crystal display device or the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
Unless otherwise specified, “parts”, “%” and “molecular weight” represent “parts by mass”, “mass%” and “weight average molecular weight”, respectively.

(Example 1)
<Color filter pattern formation (coating method)>
(1) Formation of Black Matrix An alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state. After cooling the substrate and adjusting the temperature to 23 ° C., the composition described in Table 3 below is applied on a glass substrate coater (manufactured by FS Japan Co., Ltd., trade name: MH-1600) having a slit-like nozzle. The photosensitive composition K1 which consists of was apply | coated. Subsequently, after part of the solvent was dried by VCD (vacuum drying device, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, the substrate was surrounded by EBR (edge bead remover). Unnecessary coating solution was removed and prebaked at 120 ° C. for 3 minutes to form a photosensitive layer K1 having a thickness of 2 μm.

-Preparation of photosensitive composition K1-
K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 3 below were weighed out, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Next, methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, B-CIM (2,2-bis (2-chlorophenyl) -4,5,4 ', 5-tetraphenyl-1 in the amounts shown in Table 3 below , 2′-biimidazole, manufactured by Hodogaya Chemical Co., Ltd.), NBCA (10-n-butyl-2-chloroacridone, manufactured by Kurokin Kasei Co., Ltd.), N-phenyl mercaptobenzimidazole, and surfactant 1 And added in this order at a temperature of 25 ° C. (± 2 ° C.), stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 RPM for 30 minutes, and filtered through nylon mesh # 200. The photosensitive composition K1 was prepared by the above.

Of the compositions listed in Table 3,
The composition of K pigment dispersion 1 is 13.1% by mass of carbon black (Degussa), 0.65% by mass of a dispersant represented by the following formula (6), polymer (benzyl methacrylate / methacrylic acid = 72 / 28 mol ratio random copolymer, molecular weight 37,000) 6.72% by mass, and propylene glycol monomethyl ether acetate 79.53% by mass.
The composition of the binder 2 is composed of 27% by mass of a polymer (random copolymer of benzyl methacrylate / methacrylic acid = 78/22 molar ratio, molecular weight 38,000) and 73% by mass of propylene glycol monomethyl ether acetate.
The composition of the DPHA solution is composed of 76% by mass of dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA), and 24% by mass of propylene glycol monomethyl ether acetate.
The composition of the surfactant 1 is composed of 30% by mass of the following structure 1 and 70% by mass of methyl ethyl ketone (MEK).

However, in the formula of the structure 1, the numerical values of x and y represent a molar ratio.

-Exposure process-
The photosensitive layer K1 on the substrate was exposed to a black matrix pattern corresponding to 20 mJ / m ^{2 with} a laser beam having a wavelength of 405 nm by an exposure apparatus and an exposure method described below. The exposure is performed under an N ₂ atmosphere so as to obtain a 15-step step wedge pattern (ΔOD = 0.15) and a lattice pattern in which a large number of holes having different line widths are formed. The area of was cured.

<< Exposure apparatus, exposure method >>
8-9 and 25-29 as the light irradiating means, and 1024 micromirrors 58 arranged in the main scanning direction schematically shown in FIG. 6 as the light modulating means. DMD 36 controlled to drive only 1024 × 256 rows out of 768 pairs of mirror rows arranged in the sub-scanning direction, and an optical system for imaging the light shown in FIG. 5 on the photosensitive layer The exposure apparatus 10 provided with the exposure head 30 was used.

As the set inclination angle of each exposure head 30, that is, each DMD 36, an angle slightly larger than the angle θ _{ideal at} which double exposure is performed using a usable 1024 columns × 256 rows micromirror 58 was adopted. This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
Since s = 256 and N = 2, the angle θ _ideal is about 0.45 degrees. Therefore, for example, 0.50 degrees is adopted as the set inclination angle θ.

First, the state of the exposure pattern on the exposed surface was examined in order to correct the variation in resolution and uneven exposure in double exposure. The results are shown in FIG. In FIG. 18, the pattern of light spots from the micromirror 58 usable by the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the photosensitive layer 12 with the stage 14 being stationary. showed that. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. Are shown for exposure areas 32 ₁₂ and 32 ₂₁ . In FIG. 18, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

As shown in FIG. 18, as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ from the ideal state, both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B are both. Thus, it can be seen that, in the exposure areas overlapping on the coordinate axes orthogonal to the scanning direction of the exposure head in the exposure areas 32 ₁₂ and 32 ₂₁ , an overexposed area is generated as compared with the ideal double exposure state.

The use of a set of slits 28 and a photodetector as a light spot position detection means, the position of the point P of the exposure head _{30 12} For the exposure area _{32 12} (1,1) and P (256,1), the exposure head For 30 ₂₁ , the positions of the light spots P (1,1024) and P (256, 1024) in the exposure area 32 ₂₁ are detected, and the angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head is determined. It was measured.

Using the actual inclination angle θ ′, the following equation 4
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ . T = 254 for the exposure head _{30 12,} the exposure head _{30 21} T = 255 was derived respectively. As a result, the micromirrors constituting the portions 78 and 80 covered with diagonal lines in FIG. 19 were identified as micromirrors that are not used during the main exposure.

Thereafter, the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with the oblique lines in FIG. 19 were similarly covered with the shaded areas 82 and the shaded areas in FIG. Micromirrors corresponding to the light spots constituting the region 84 were identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. It was controlled not to be involved.
As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ , an ideal double exposure is performed in each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. Thus, the total area of the overexposed region and the underexposed region can be minimized.

-Development process-
After the exposure is completed, pure water is sprayed onto the surface of the photosensitive layer K1 using a shower nozzle so as to be uniformly moistened, and then a KOH developer (KOH, containing a nonionic surfactant, trade name: CDK-1, FUJIFILM Electronics Materials Co., Ltd.) shower development at 23 ° C. for 80 seconds at a flat nozzle pressure of 0.04 MPa, and then spray ultrapure water at a pressure of 9.8 MPa using an ultrahigh pressure cleaning nozzle. The residue was removed to obtain a black matrix pattern. Thereafter, heat treatment was performed at 220 ° C. for 30 minutes.

(2) Formation of red (R) pixels The following photosensitive composition R1 having the composition described in Table 4 below is used for the substrate on which the black matrix is formed, and heat treatment is performed in the same process as the formation of the black matrix. An R pixel was formed. The R1 photosensitive layer thickness was 1.5 μm, and the coating amount of the pigment (CI Pigment Red 254) was 0.274 g / m ² .

-Preparation of photosensitive composition R1-
R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 4 below were weighed out, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Subsequently, methyl ethyl ketone, cyclohexanone, binder 1, DPHA solution, B-CIM (manufactured by Hodogaya Chemical Co., Ltd.), NBCA (manufactured by Kurokin Kasei Co., Ltd.), N-phenyl mercaptobenzimidazole, and phenothiazine in the amounts shown in Table 4 below. Were added in this order at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 30 minutes. Furthermore, the surfactant 1 in the amount shown in Table 4 below was weighed, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through a nylon mesh # 200. By the above, photosensitive composition R1 was prepared.

Of the compositions listed in Table 4,
The composition of R pigment dispersion 1 is C.I. I. Pigment Red 254 (manufactured by Ciba Specialty Chemicals) 8% by mass, dispersant 0.8% by mass represented by the formula (6), polymer (random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio) 8% by mass and 83% by mass of propylene glycol monomethyl ether acetate.
The composition of R pigment dispersion 2 is C.I. I. Pigment Red 254 (manufactured by Ciba Specialty Chemicals) 5.3 mass%, acrylic acid mono (dimethylaminopropyl) amide / methacrylic acid (polyethylene glycol monomethyl ether) ester / methacrylic acid (polymethyl methacrylate-containing alcohol) ester 1.6 mass %, Propylene glycol monomethyl ether acetate 93% by mass.
The composition of the binder 1 is composed of 27% by mass of a polymer (random copolymer of benzyl methacrylate / methacrylic acid / methyl methacrylate = 38/25/37, molecular weight 38,000) and 73% by mass of propylene glycol monomethyl ether acetate.

-Exposure process and development process-
The photosensitive layer R1 on the substrate was exposed in the same manner as the photosensitive layer K1. The exposure amount was 20 mJ / cm ² . Further, for evaluation, the photosensitive layer R1 is similarly formed on a substrate on which a black matrix is not formed, and a color filter pattern, a resolution evaluation pattern (a pattern in which a large number of holes having different diameters are formed), and The same processing was performed using the step wedge pattern. Then, it developed similarly to the black matrix and heat-processed.

[Evaluation]
The formed red (R) color filter pattern (pixel) was evaluated for exposure sensitivity, resolution, and unevenness by the following methods. The results are shown in Table 10 below.

<Exposure sensitivity>
In the obtained red (R) color filter pattern (pixels), the thickness of the cured region of the remaining photosensitive layer was measured. Subsequently, a sensitivity curve is obtained by plotting the relationship between the irradiation amount of the laser beam and the thickness of the cured layer. From the sensitivity curve thus obtained, the thickness of the cured region on the substrate is 1.5 μm, and the amount of light energy when the surface of the cured region is a glossy surface is the amount of light energy necessary to cure the photosensitive layer. .

<Resolution>
The surface of the obtained red (R) resolution evaluation pattern-formed substrate was observed with an optical microscope, and the minimum hole diameter with no residual film in the hole portion of the cured layer pattern was measured. . The smaller the numerical value, the better the resolution.

(3) Formation of green (G) pixels The following photosensitive composition G1 having the composition shown in Table 5 below is used on the substrate on which the black matrix and red (R) pixels are formed, and is similar to the formation of the black matrix. Through this process, a heat-treated green (G) pixel was formed. The film thickness of the G1 photosensitive layer is 1.4 μm, the coating amount of pigment (CI Pigment Green 36) is 0.355 g / m ² , and the coating amount of pigment (CI Pigment Yellow 139) is 0.052 g. / M ² . It was exposed, developed and heat treated in the same manner as the black matrix. The exposure amount was equivalent to 40 mJ / cm ² .

-Preparation of photosensitive composition G1-
G pigment dispersion 1, Y pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts shown in Table 5 below were weighed out, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Next, the amounts of methyl ethyl ketone, binder 1, DPHA solution, B-CIM (Hodogaya Chemical Co., Ltd.), NBCA (Kurokin Kasei Co., Ltd.), N-phenyl mercaptobenzimidazole, and phenothiazine in the amounts shown in Table 5 below are measured. Were added in this order at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 30 minutes. Further, the surfactant 1 in the amount shown in Table 5 below was weighed, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through a nylon mesh # 200. The photosensitive composition G1 was prepared by the above.

In addition, among the compositions described in Table 5,
The composition of G pigment dispersion 1 is C.I. I. Pigment Green 36 (manufactured by Toyo Ink Manufacturing Co., Ltd., dispersion) 18% by mass, polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 38,000) 12% by mass, cyclohexanone 35% %, Propylene glycol monomethyl ether acetate 35% by mass.
The composition of the Y pigment dispersion 1 is C.I. I. Pigment Yellow 139 (manufactured by Toyo Ink Mfg. Co., Ltd., trade name: Pariolol Yellow L1820) 18% by mass, polymer (random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 38,000) 15 It consists of 15% by mass of cyclohexanone, 52% by mass of propylene glycol monomethyl ether acetate.

(4) Formation of blue (B) pixel On the substrate on which the black matrix, red (R) pixel, and green (G) pixel are formed, the following photosensitive composition B1 having the composition shown in Table 6 below is used. Through the same process as the formation of the black matrix, heat-treated blue (B) pixels were formed, and a target color filter was produced.
The film thickness of the B1 photosensitive layer was 1.4 μm, and the coating amount of pigment (CI Pigment Blue 15: 6) was 0.29 g / m ² . Exposure, development, and heat treatment were performed in the same manner as the K photosensitive layer. The exposure amount was 50 mJ / cm ² .

-Preparation of photosensitive composition B1-
B pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 6 below were weighed out, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Next, the amounts of methyl ethyl ketone, binder 2, DPHA solution, B-CIM (made by Hodogaya Chemical Co., Ltd.), NBCA (made by Kurokin Kasei Co., Ltd.), N-phenyl mercaptobenzimidazole, and phenothiazine are measured in the amounts shown in Table 6 below. And added in this order at a temperature of 25 ° C. (± 2 ° C.) and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. Furthermore, the surfactant 1 in the amount shown in Table 6 below was weighed out, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 RPM for 5 minutes, and filtered through nylon mesh # 200. By the above, photosensitive composition B1 was prepared.

Of the compositions listed in Table 6,
The composition of B pigment dispersion 1 is C.I. I. Pigment Blue 15: 6 (manufactured by Toyo Ink Mfg. Co., Ltd.) 10% by mass, Dispersant 1 (EFKA-6745, EFKA ADDITIVES B.V) 0.5% by mass, Dispersant 2 (Disparon DA-725, Enomoto) (Made by Kasei Co., Ltd.) 0.63 mass%, polymer (random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 38,000) 12.5 mass%, propylene glycol monomethyl ether acetate 76. It consists of 37% by mass.

(Example 2)
[Color filter pattern formation (film method)]
<Production of photosensitive transfer material>
On a 75 μm-thick polyethylene terephthalate (PET) film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, the colored photosensitive resin composition K1 is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a dry layer are dried on the temporary support. A photosensitive resin layer having a thickness of 2 μm was provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded.
Thus, a photosensitive resin transfer material K1 in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer were integrated was produced.

-Coating solution for thermoplastic resin layer: Preparation of formulation H1-
11.1 parts by mass of methanol, 6.36 parts by mass of propylene glycol monomethyl ether acetate, 52.4 parts by mass of methyl ethyl ketone, methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio)) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.) 5.83 parts by mass, styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio)) = 63 / 37, molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts by mass, compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., 2,2-bis [ 4- (methacryloxypolyethoxy) phenyl] propane) 9.1 parts by weight, and 10.54 parts by weight of the surfactant. A thermoplastic resin layer coating liquid was prepared.

-Coating solution for intermediate layer: Preparation of formulation P1-
PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550) 32.2 parts by mass, polyvinylpyrrolidone (manufactured by ASP Japan Co., Ltd., K-30) 14.9 parts by mass, distillation An intermediate layer coating solution comprising 524 parts by mass of water and 429 parts by mass of methanol was prepared.

Next, the photosensitive composition K1 used in the production of the photosensitive transfer material K1 was changed to the following photosensitive compositions R101, G101, and B101 having the compositions shown in Tables 7 to 9 above. Photosensitive transfer materials R101, G101, and B101 were produced by the same method as described above.
In addition, the preparation method of photosensitive composition R101, G101, and B101 is based on the preparation method of the said photosensitive composition R1, G1, and B1, respectively.

(1) Formation of red (R) pixel An alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by shower, and after washing with pure water shower, a silane cup A ring solution (0.3% by mass aqueous solution of N-β (aminoethyl) γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed with a shower for 20 seconds and washed with pure water by shower. This substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device and sent to the next laminator.
After peeling off the protective film of the photosensitive resin transfer material R101, a laminator (Lamic II type, manufactured by Hitachi Industries, Ltd.) was used to heat the substrate heated to 100 ° C, with a rubber roller temperature of 130 ° C and a linear pressure of 100N. / Cm, laminating at a conveyance speed of 2.2 m / min.

-Exposure process-
After the protective film is peeled off, the exposure layer of Example 1 is used to irradiate a laser beam having a wavelength of 405 nm by irradiating the same step wedge pattern, stripe shape and dot shape as in Example 1, and then exposing the photosensitive layer. Some areas of were cured. In the same manner as in Example 1, in addition to the color filter pattern, a color filter pattern, a sensitivity evaluation pattern, and a resolution evaluation pattern were also formed on a substrate on which no black matrix was formed. The exposure amount was 20 mJ / cm ² and was performed in an air atmosphere.

-Development process-
Next, in a triethanolamine developer (2.5% by mass of triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer.
Subsequently, a sodium carbonate-based developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer, trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) was used for shower development at 35 ° C. for 35 seconds and a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer to obtain a patterned pixel.
Subsequently, detergent (phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer included, trade name: T-SD1, manufactured by Fuji Photo Film Co., Ltd., or sodium carbonate, phenoxyoxyethylene surfactant Containing, trade name: T-SD2, manufactured by Fuji Photo Film Co., Ltd.), removing residue with a rotating brush having a shower and nylon bristles at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa. A pixel of (R) was obtained. Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ^{2 with} an ultrahigh pressure mercury lamp from the resin layer side, and then heat-treated (baked) at 220 ° C. for 15 minutes.
The film thickness of the R101 photosensitive layer was 2.0 μm, and the coating amount of pigment (CI Pigment Red 254) was 0.314 g / m ² .
Here, in the same manner as in Example 1, the exposure sensitivity, resolution, and unevenness of the R color filter pattern were evaluated. The results are shown in Table 10 below.
The substrate on which the red (R) pixels were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating device.

(2) Formation of Green (G) Pixel Using the photosensitive transfer material G101, a heat-treated green (G) pixel was produced in the same process as the photosensitive transfer material R101. The exposure amount was 40 mJ / cm ² .
The photosensitive layer thickness of G101 is 2.0 μm, the coating amount of pigment (CI Pigment Green 36) is 0.396 g / m ² , and the coating amount of pigment (CI Pigment Yellow 139) is 0.0648 g. / M ² .
The substrate on which the red (R) and green (G) pixels are formed is again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling solution is not used and sent to the substrate preheating device. It was.

(3) Formation of Blue (B) Pixel Using the photosensitive transfer material B101, a heat-treated blue (B) pixel was produced in the same process as the photosensitive transfer material R101. The exposure amount was 50 mJ / cm ² .
The B101 photosensitive layer thickness was 2.0 μm, and the coating amount of pigment (CI Pigment Blue 15: 6) was 0.32 g / m ² .
The substrate on which the red (R), green (G), and blue (B) pixels are formed is again cleaned with a brush as described above, and after washing with pure water, the substrate is used without using a silane coupling liquid. Sent to preheater.

(4) Formation of Black (K) Image and Black Matrix Using the photosensitive transfer material K1, in the same process as the photosensitive transfer material R101, a heat-treated black (K) image (the frame portion of the color filter) Formation) and a black matrix portion. The exposure amount was 80 mJ / cm ² .

[Evaluation]
<Coating unevenness>
For evaluation, the substrate immediately after the formation of only the red (R) photosensitive layer was irradiated obliquely with a Na lamp in a dark room and visually observed to determine the presence or absence of unevenness.
<Display unevenness>
The substrate with pixels for which patterning was completed (only a red (R) photosensitive layer was formed for evaluation) was irradiated obliquely with a Na lamp in a dark room and visually observed to determine the presence or absence of unevenness. .
In addition, evaluation of these nonuniformity showed the example of red (R) from a viewpoint that nonuniformity is easy to observe.

From the results in Table 10, it was confirmed that the color filter patterns of Examples 1 and 2 had little coating unevenness and display unevenness, high exposure sensitivity and resolution, and a good color filter could be produced.

[Production and Evaluation of Liquid Crystal Display]
Using the color filters of Examples 1 and 2, a reflective and transmissive liquid crystal display device having an LED backlight was produced. It confirmed that the liquid crystal display device using the color filter of Examples 1-2 showed a favorable display characteristic.

(Example 3)
[Color filter pattern formation] (for TV, coating method)
(1) Formation of black matrix A black matrix was formed in the same manner as in Example 1.

(2) Formation of Red (R) Pixel Using the photosensitive composition R2 having the composition described in Table 11 below, it was formed in the same manner as in Example 1. The coating film thickness was 1.6 μm.
Of the compositions listed in Table 11,
The composition of the R pigment dispersion 3 is C.I. I. 18 parts of Pigment Red 177 (manufactured by Ciba Specialty Chemicals), 12 parts of polymer (random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio), and 70 parts of propylene glycol monomethyl ether acetate.

(3) Formation of Green (G) Pixel A photosensitive composition G2 having the composition described in Table 12 below was used and formed in the same manner as in Example 1. The coating film thickness was 1.6 μm.
Of the compositions shown in Table 12, Y Pigment Dispersion 2 was manufactured by using Gokoku Color Co., Ltd., trade name: CF Yellow EX3393.

(4) Formation of Blue (B) Pixels A photosensitive composition B2 having the composition described in Table 13 below was used and formed in the same manner as in Example 1. The coating film thickness was 1.6 μm.
Of the compositions listed in Table 13,
-As the B pigment dispersion 2, the product name: CF Blue EX3357 manufactured by Mikuni Color Co., Ltd. was used.
-As the B pigment dispersion 3, the product name: CF blue EX3383 made from Mikuni Color Co., Ltd. was used.
The composition of the binder 3 is 27% by mass (random copolymer of benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio, molecular weight 38,000), and 73% by mass of propylene glycol monomethyl ether acetate. .

Example 4
[Color filter pattern formation] (for TV, film method)
(1) Formation of black matrix A black matrix was formed in the same manner as in Example 2. However, the formation order was black (black matrix) first, and the black matrix and the peripheral frame portion were formed.

(2) Formation of Red (R) Pixel Using the photosensitive composition R102 having the composition described in Table 14 below, the pixel was formed in the same manner as in Example 2. The coating film thickness was 2.0 μm.
In addition, among the compositions described in Table 14, the phosphate ester special activator 1 used was trade name: HIPLAAD ED152 manufactured by Enomoto Kasei Co., Ltd.

(3) Formation of Green (G) Pixel Using the photosensitive composition G102 having the composition described in Table 15 below, it was formed in the same manner as in Example 2. The coating film thickness was 2.0 μm.

(4) Formation of Blue (B) Pixels A photosensitive composition B102 having the composition described in Table 16 below was used and formed in the same manner as in Example 2. The coating film thickness was 1.6 μm.

  For Examples 3 and 4, exposure sensitivity, resolution, and unevenness were evaluated in the same manner as in Examples 1 and 2. The results are shown in Table 17.

From the results shown in Table 17, it was confirmed that the color filter patterns of Examples 3 and 4 had little coating unevenness and display unevenness, high exposure sensitivity and resolution, and a good color filter could be produced.

<Evaluation of edge roughness>
Of the black matrix formed in a stripe shape in Example 3, five arbitrary positions of a line having a line width of 20 μm were observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 ×). Of the edge positions in the field of view, find the absolute value of the difference between the most swollen part (peak) and the narrowest part (valley) and calculate the average value of the five observed points. Roughness. The edge roughness is preferably as the value is small because it exhibits good performance. The results are shown in Table 18.

(Comparative Example 1)
In the exposure apparatus of Embodiment 1, the set inclination angle θ is calculated with N = 1 based on the above equation 3, and the natural number T closest to the value t satisfying the relationship of t tan θ ′ = 1 is derived based on the above equation 4. A striped black matrix was formed in the same manner as in Example 3 except that heavy exposure (N = 1) was performed, and edge roughness was evaluated by the above method. The results are shown in Table 18.

An example of the state of exposure of the exposed surface in Comparative Example 1 is shown in FIG. In FIG. 35, the light spot from the usable micromirror 58 of the DMD 36 of one exposure head (for example, 30 ₁₂ ) projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary. The group pattern was shown. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. For one exposure area (eg, 32 ₁₂ ).
An example of pattern distortion appearing on an exposed surface as a result of a deviation from an ideal state of the one exposure head (for example, 30 ₁₂ ), and an inclination of each pixel row projected on the exposed surface An “angular distortion” occurs in which the angle is not uniform. The angular distortion appearing in the example of FIG. 35 is a distortion in which the tilt angle with respect to the scanning direction is larger in the left column of the figure and smaller in the right column of the figure. As a result of this angular distortion, an overexposed area is formed on the exposed surface shown on the left side of the figure, and an underexposed area is formed on the exposed surface shown on the right side of the figure.

From the results shown in Table 18, compared to Comparative Example 1, the black matrix of Example 3 has a small edge roughness and a high-definition black matrix pattern because the variation in resolution and uneven exposure in double exposure are corrected. I knew it was possible.

The color filter manufactured by the method for manufacturing a color filter of the present invention has good display characteristics in both the transmissive mode and the reflective mode, and is suitable for liquid crystal display devices (LCD) such as portable terminals and portable game machines. In addition, it is also suitably used for liquid crystal display devices (LCD) such as notebook computers and television monitors, PALC (plasma address liquid crystal), and plasma displays. In addition to the color filter exemplified here, a spacer can be formed by overlapping at least one of RGB colors described in Japanese Patent Application Laid-Open No. 11-248921 and Japanese Patent No. 3255107.

FIG. 1 is a perspective view showing an appearance of an example of an exposure apparatus. FIG. 2 is a perspective view showing an example of the configuration of the scanner of the exposure apparatus. FIG. 3A is a plan view showing an exposed region formed on the exposed surface of the photosensitive layer. FIG. 3B is a plan view showing an arrangement of exposure areas by each exposure head. FIG. 4 is a perspective view showing an example of a schematic configuration of the exposure head. FIG. 5A is a top view showing an example of a detailed configuration of the exposure head. FIG. 5B is a side view showing an example of a detailed configuration of the exposure head. FIG. 6 is a partially enlarged view showing an example of the DMD of the exposure apparatus of FIG. FIG. 7A is a perspective view for explaining the operation of the DMD. FIG. 7B is a perspective view for explaining the operation of the DMD. FIG. 8 is a perspective view showing an example of the configuration of the fiber array light source. FIG. 9 is a front view showing an example of the arrangement of light emitting points in the laser emitting section of the fiber array light source. FIG. 10 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is an exposure head mounting angle error and pattern distortion. FIG. 11 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit. FIG. 12 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 13 is an explanatory diagram showing a state in which unevenness generated in a pattern on an exposed surface is improved as a result of using only selected micromirrors for exposure. FIG. 14 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift between adjacent exposure heads. FIG. 15 is a top view showing a positional relationship between an exposure area by two adjacent exposure heads and a corresponding slit. FIG. 16 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 17 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 14 are actually moved and the unevenness in the pattern on the exposed surface is improved. FIG. 18 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift and a mounting angle error between adjacent exposure heads. FIG. 19 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG. FIG. 20A is an explanatory diagram showing an example of magnification distortion. FIG. 20B is an explanatory diagram showing an example of beam diameter distortion. FIG. 21A is an explanatory view showing a first example of reference exposure using a single exposure head. FIG. 21B is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 22 is an explanatory diagram showing a first example of reference exposure using a plurality of exposure heads. FIG. 23A is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 23B is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 24 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads. FIG. 25 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 26 is an example of a plan view showing the configuration of the combined laser light source. FIG. 27 is an example of a plan view showing the configuration of the laser module. FIG. 28 is an example of a side view showing the configuration of the laser module shown in FIG. FIG. 29 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 30 is an example of a perspective view showing a configuration of a laser array. FIG. 31A is an example of a perspective view showing a configuration of a multi-cavity laser. FIG. 31B is an example of a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. 31A are arranged in an array. FIG. 32 is an example of a plan view showing another configuration of the combined laser light source. FIG. 33 is an example of a plan view showing another configuration of the combined laser light source. FIG. 34A is an example of a plan view showing another configuration of the combined laser light source. FIG. 34B is an example of a cross-sectional view along the optical axis of FIG. 34A. FIG. 35 is an explanatory diagram showing an example of unevenness generated in the pattern on the exposed surface due to “angle distortion” in which the inclination angle of each pixel column is not uniform in Comparative Example 1.

Explanation of symbols

B1 to B7 Laser beam L1 to L7 Collimator lens LD1 to LD7 GaN-based semiconductor laser 10 Exposure apparatus 12 Photosensitive layer (photosensitive material)
DESCRIPTION OF SYMBOLS 14 Moving stage 18 Installation stand 20 Guide 22 Gate 24 Scanner 26 Sensor 28 Slit 30 Exposure head 32 Exposure area 36 Digital micromirror device (DMD)
38 Fiber array light source 58 Micro mirror (picture element)
60 laser module 62 multimode optical fiber 64 optical fiber 66 laser emitting section 110 heat block 111 multicavity laser 113 rod lens 114 lens array 140 laser array 200 condenser lens

Claims (19)

A photosensitive layer forming step of forming at least a photosensitive layer on the surface of the substrate using a photosensitive composition containing a binder, a polymerizable compound, a colorant, and a photopolymerization initiator;
For the photosensitive layer,
A light irradiating means, and n (where n is a natural number of 2 or more) two-dimensionally arranged picture elements that receive and emit light from the light irradiating means, and according to the pattern information, An exposure head provided with a light modulation means capable of controlling a picture element portion, the exposure head being arranged so that a column direction of the picture element portion forms a predetermined set inclination angle θ with respect to a scanning direction of the exposure head Using the head
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
An exposure step of performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction; and
A development step of developing the photosensitive layer exposed in the exposure step.   Exposure is performed by a plurality of exposure heads, and a used pixel part specifying means is used for exposing a pixel part related to exposure of a head-to-head connection area, which is an overlapping exposure area on an exposed surface formed by the plurality of exposure heads. The method for manufacturing a color filter according to claim 1, wherein the pixel portion used for realizing N-fold exposure in the inter-head connection region is designated.   Picture element part in which exposure is performed by a plurality of exposure heads and the used picture element part specifying means is involved in exposure other than the inter-head joint area which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads 3. The method for manufacturing a color filter according to claim 2, wherein the pixel portion used for realizing N double exposure in an area other than the inter-head connecting area is designated. Use pixel part designation means,
A light spot position detecting means for detecting a light spot position on the exposed surface as a pixel unit generated by the pixel part and constituting an exposure area on the exposed surface;
4. The color filter according to claim 1, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing N double exposure based on a detection result by the light spot position detection unit. 5. Production method.   5. The use picture element specifying means includes a slit and a photodetector as a light spot position detection means, and an arithmetic unit connected to the photodetector as a picture element selection means. A method for producing a color filter.   6. The method for producing a color filter according to claim 1, wherein N of N double exposure is a natural number of 3 or more and 7 or less.   The method for producing a color filter according to claim 1, wherein the light modulation means is a spatial light modulation element.   The method for producing a color filter according to claim 7, wherein the spatial light modulation element is a digital micromirror device (DMD). The set inclination angle θ is N of N multiple exposure numbers, the number s of pixel portions in the column direction, the interval p in the column direction of the pixel portions, and the scanning direction of the exposure head when the exposure head is inclined. to the column direction of the pitch δ of pixel parts along a direction orthogonal, the following equation with respect to theta _ideal satisfying spsinθ _ideal ≧ Nδ, claim 1 is set so as to satisfy the relation of θ ≧ θ _ideal 8 The manufacturing method of the color filter in any one of.   The method for producing a color filter according to claim 1, wherein the light irradiating means can synthesize and irradiate two or more lights.   The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system for condensing the laser beams irradiated from the plurality of lasers and converging them on the incident end face of the multimode optical fiber. Item 11. A method for producing a color filter according to any one of Items 1 to 10.   The method for producing a color filter according to any one of claims 1 to 11, wherein the photosensitive layer is formed by applying a photosensitive composition to the surface of a substrate and drying.   Using a photosensitive transfer material having a photosensitive transfer layer made of a photosensitive composition on a support, the photosensitive layer is laminated on the substrate so that the photosensitive transfer layer and the substrate are in contact with each other, Then, the manufacturing method of the color filter in any one of Claim 1 to 11 formed by peeling a support body.   The method for producing a color filter according to claim 1, wherein the photosensitive composition is colored at least in black (K).   For each color of R, G, and B in a predetermined arrangement on the surface of the substrate, using a photosensitive composition colored in at least three primary colors of red (R), green (G), and blue (B) The method for producing a color filter according to claim 1, wherein the color filter is formed by sequentially repeating the photosensitive layer forming step, the exposure step, and the developing step.   At least pigment C.I. I. Pigment Red 254 is colored green (G) with pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 139 and at least a pigment C.I. I. The method for producing a color filter according to claim 15, wherein Pigment Blue 15: 6 is used.   Pigment to red (R) coloring C.I. I. Pigment red 254 and pigment C.I. I. Pigment Red 177 at least one pigment is changed to a green (G) coloring pigment C.I. I. Pigment green 36 and pigment C.I. I. Pigment Yellow 150 and at least blue (B) pigment C.I. I. Pigment blue 15: 6 and pigment C.I. I. The method for producing a color filter according to claim 15, wherein at least one pigment of pigment violet 23 is used.   A color filter manufactured by the method for manufacturing a color filter according to claim 1. A display device using the color filter according to claim 18.